Hydrocarbon Substrates Research Articles

Enantioselective organocatalysis using SOMO activation.

The asymmetric α-addition of relatively nonpolar hydrocarbon substrates, such as allyl and aryl groups, to aldehydes and ketones remains a largely unsolved problem in organic synthesis, despite the wide potential utility of direct routes to such products. We reasoned that well-established chiral amine catalysis, which activates aldehydes toward electrophile addition by enamine formation, could be expanded to this important reaction class by applying a single-electron oxidant to create a transient radical species from the enamine. We demonstrated the concept of singly occupied molecular orbital (SOMO) activation with a highly selective α-allylation of aldehydes, and we here present preliminary results for enantioselective heteroarylations and cyclization/halogenation cascades.

Hexafluorothioacetone based synthesis of fluorinated heterocycles

Cycloadducts of hexafluorothioacetone (HFTA) were prepared in high yield by a CsF catalyzed reaction between readily available 2,2,4,4-tetrakis-(trifluoromethyl)-1,3-dithietane (as a source of HFTA) with conjugated electron-rich hydrocarbon dienes, such as cyclopentadiene, 2,3-dimethylbuta-1,3-diene, cyclohexa-1,3-diene or (1 Z,3 Z)-cyclohepta-1,3-diene. Cyclohexa-1,4- and (1 Z,5 Z)-cycloocta-1,5-dienes, also undergo the reaction with in situ generated HFTA, but form the products of insertion of HFTA into the C–H bond of the diene as a result of ene-reaction. The highly selective reaction of HFTA with (1 Z,3 Z,5 Z)-cyclohepta-1,3,5-triene and (1 Z,3 Z,5 Z,7 Z)-cycloocta-1,3,5,7-tetraene leads to the formation of cycloadducts derived from exclusive addition of thioacetone to the corresponding bicyclic isomers—bicyclo[4.1.0]hepta-2,4-diene or bicyclo[4.2.0]octa-2,4,7-triene, respectively. The corresponding cycloadducts of HFTA with 2,3-dimethylbutadiene-1,3-cyclohexa-1,3-cyclohexa-1,4-dienes and (1 Z,3 Z,5 Z)-cyclohepta-1,3,5-triene were also prepared by direct reaction of sulfur/hexafluoropropene/KF and the corresponding hydrocarbon substrate at 35–45 °C in DMF.

Insight into heterogeneity in cell-surface hydrophobicity and ability to degrade hydrocarbons among cells of two hydrocarbon-degrading bacterial populations

The sequential bacterial adherence to hydrocarbons (BATH) of successive generations of hydrophobic fractions of Paenibacillus sp. R0032A and Burkholderia cepacia gave rise to bacterial populations of increasing cell-surface hydrophobicity. Thus, hydrophobicity of the first generation (H1) was less than that of the second generation (H2), which was less than that of the third generation (H3). Beyond H3, the hydrophobic populations became less stable and tended to lyse in hexadecane after violent (vortex) agitation, resulting in an apparent decline in BATH value. The exhaustively fractionated aqueous-phase population (L) was very hydrophilic. The overall cell-surface distribution of the population was L < parental strain < H1 < H2 < H3. The ability to degrade crude oil, hexadecane, or phenanthrene matched the degree of cell-surface hydrophobicity: L < P < H1 < H2 < H3. Thus, in natural populations of hydrocarbon-degrading Paenibacillus sp. R0032A and B. cepacia, there is a heterogeneity in the hydrophobic surface characteriistics that affects the ability of cells to use various hydrocarbon substrates.

Self-organization of diamond nanocrystallites in a low-pressure microwave plasma

The self-organization effect is found in diamond nanocrystallites that arise in polymer-like hydrocarbon films growing in the nonequilibrium microwave plasma of volatile carboniferous materials at a low substrate temperature. The nature of this effect (specifically, the conditions of formation of the hydrocarbon substrate, its role during diamond nanocrystallite growth, and ways of controlling the size and concentration of the crystallites) is studied.

Selective catalytic oxidation of alkylaromatic molecules by nanosize water droplets containing Co2+ species in supercritical carbon dioxide fluid

Stabilized nano-sized water droplet carrying water-soluble Co2+ species is employed as a new catalyst system for the oxidation of the alkyl aromatics in the presence of a fluorinated surfactant. This stable system contains no labile C--H structure and can facilitate excellent mixing of catalytic Co(II)/NaBr species, hydrocarbon substrates and oxygen in supercritical carbon dioxide fluid, which is demonstrated to be an excellent alternative solvent system to acetic acid or nitric acid for air oxidation of a number of alkyl aromatic hydrocarbons using Co(II) species at mild conditions. As a result, potential advantages of this ‘greener’ catalytic method including safer operation, easier separation and purification, higher catalytic activity with selectivity and without using corrosive or oxidation unstable solvent are therefore envisaged.

Synergetic effects of cell immobilization in polyurethane foam and use of thermotolerant strain on degradation of mixed hydrocarbon substrate by Prototheca zopfii

The synergetic effects of an immobilized cell system in an oleophilic polyurethane foam (PUF) and use of a thermotolerant strain on degradation of hydrocarbons by colorless green microalga Prototheca zopfii are reported. Two strains of P. zopfii, i.e. thermotolerant RND 16 and non-thermotolerant ATCC30253, were immobilized in PUF to compare their abilities to biodegrade a mixed hydrocarbon substrate (MHS) containing aliphatic and polycyclic aromatic hydrocarbons (PAHs), as a function of temperature. The thermotolerant strain RND 16 degraded MHS at 35°C, while ATCC30253 did not degrade hydrocarbons at temperatures higher than 30°C. Immobilization of P. zopfii in PUF resulted in shortened lag for growth-associated biodegradation of n-alkanes in MHS, the effect of which was most significant in cultures of RND 16 at 25°C. Nevertheless, the decrease in the amount of degraded PAHs was caused by PUF immobilization and the level of this decrease was marked in the cultures of RND 16, in which rate and extent of n-alkane degradation were higher than for ATCC30253.

The classical kinetic model for radical chain oxidation of hydrocarbon substrates initiated by bimolecular hydroperoxide decomposition

AbstractKinetic modeling of the low‐temperature (typically T ⩽ 200°C) thermal aging of polymers is a problem of great technological importance, owing to the continuously increasing needs of industry in terms of reliable methods for lifetime prediction. In the temperature domain under consideration, for most hydrocarbon substrates, oxidation proceeds by a radical chain reaction initiated by bimolecular hydroperoxide decomposition. In other words, the reaction generates its own initiator, which explains its strong autoaccelerated character. The most pertinent model is, to our opinion, the model elaborated by Tobolsky et al. (J Am Chem Soc 1950, 72, 1942) in the early 1950s. This model is, however, based on three questionable assumptions: the existence of a stationary state for radical concentrations (hypothesis S), the presence of oxygen in excess (hypothesis E), and the fact that the onset of steady state can be observed in the domain of low conversions, where the substrate consumption can be neglected (hypothesis L). One hypothesis (S) lacks consistency. A sounder alternative, which does not modify significantly the mathematical expressions of the model, will be proposed. The other hypotheses (E and L) can be justified in certain cases, but the limits of their domain of validity were never established to our knowledge. It is tried, here, to express these limits in function of fundamental parameters: rate constants and concentrations of reactants. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38:666–676, 2006

Genome sequence of the ubiquitous hydrocarbon-degrading marine bacterium Alcanivorax borkumensis

Alcanivorax borkumensis is a cosmopolitan marine bacterium that uses oil hydrocarbons as its exclusive source of carbon and energy. Although barely detectable in unpolluted environments, A. borkumensis becomes the dominant microbe in oil-polluted waters. A. borkumensis SK2 has a streamlined genome with a paucity of mobile genetic elements and energy generation–related genes, but with a plethora of genes accounting for its wide hydrocarbon substrate range and efficient oil-degradation capabilities. The genome further specifies systems for scavenging of nutrients, particularly organic and inorganic nitrogen and oligo-elements, biofilm formation at the oil-water interface, biosurfactant production and niche-specific stress responses. The unique combination of these features provides A. borkumensis SK2 with a competitive edge in oil-polluted environments. This genome sequence provides the basis for the future design of strategies to mitigate the ecological damage caused by oil spills.Supplementary informationThe online version of this article (doi:10.1038/nbt1232) contains supplementary material, which is available to authorized users.

Mechanistic studies of the oxidative N-dealkylation of a substrate tethered to carboxylate-bridged diiron(II) complexes, [Fe2(mu-O2CAr(Tol))2(O2CAr(Tol))2(N,N-Bn2en)2

Carboxylate-bridged diiron(II) centers activate dioxygen for the selective oxidation of hydrocarbon substrates in bacterial multicomponent monooxygenases. Synthetic analogues of these systems exist in which substrate fragments tethered to the diiron(II) core through attachment to an N-donor ligand are oxidized by transient species that arise following the introduction of O2 into the system. The present study describes the results of experiments designed to probe mechanistic details of these oxidative N-dealkylation reactions. A series of diiron(II) complexes with ligands N,N-(4-R-Bn)Bnen, where en is ethylenediamine, Bn is benzyl, and R-Bn is benzyl with a para-directing group R = Cl, F, CH3, t-Bu, or OCH3, were prepared. A Hammett plot of the oxygenation product distributions of these complexes, determined by gas chromatographic analysis, reveals a small positive slope of rho = +0.48. Kinetic isotope effect (KIE(intra)) values for oxygenation of [Fe2(mu-O2CAr(Tol))2(O2CAr(Tol))2(N,N-(C6H5CDH)2en)2] and [Fe2(mu-O2CAr(Tol))2(O2CAr(Tol))2(N,N-(C6H5CD2)(C6H5CH2)en)2] are 1.3(1) and 2.2(2) at 23 degrees C, respectively. The positive slope rho and low KIE(intra) values are consistent with a mechanism involving one-electron transfer from the dangling nitrogen atom in N,N-Bn2en to a transient electrophilic diiron intermediate, followed by proton transfer and rearrangement to eliminate benzaldehyde.

Production of Biosurfactant Using Different Hydrocarbons by Pseudomonas aeruginosa EBN-8 Mutant

The present investigation dealt with the use of previously isolated and studied gamma-ray mutant strain Pseudomonas aeruginosa EBN-8 for the production of biosurfactant by using different hydrocarbon substrates viz. n-hexadecane, paraffin oil and kerosene oil, provided in minimal medium, as the sole carbon and energy sources. The batch experiments were conducted in 250 mL Erlenmeyer flasks, containing 50 mL minimal salt media supplemented with 1% (w/v) hydrocarbon substrate, inoculated by EBN-8 and incubated at 37 degrees C and 100 rpm in an orbital shaker. The sampling was done on 24 h basis for 10 d. The surface tension of cell-free culture broth decreased from 53 to 29 mN/m after 3 and 4 d of incubation when the carbon sources were paraffin oil and n-hexadecane, respectively. The largest reduction in interfacial tension from 26 to 0.4 mN/m was observed with n-hexadecane, while critical micelle dilution was obtained as 50 x CMC for paraffin oil as carbon source. When grown on n-hexadecane and paraffin oil, the EBN-8 mutant strain gave 4.1 and 6.3 g of the rhamnolipids/L, respectively. These surface-active substances subsequently allowed the hydrocarbon substrates to disperse readily as emulsion in aqueous phase.

Deactivation mechanisms of chloroperoxidase during biotransformations

Inactivation mechanisms of chloroperoxidase (CPO) from Caldariomyces fumago have been investigated with the aim of improving the practical utility of CPO for hydrocarbon oxidation. Deactivation studies in the presence of oxidants (i.e., hydrogen peroxide and t-butyl hydroperoxide) indicated that CPO lost oxidation activity toward hydrocarbon substrates during dismutation of hydrogen peroxide. The loss of enzyme activity was accompanied by the apparent destruction of the heme rather than aggregation or denaturation of the apo-protein. The decrease of enzyme activity was significantly retarded by adding the radical scavenger t-butyl alcohol at pH 4.1, or by optimizing the reaction pH. CPO retained greatest oxidation activity at pH 5-6, which may produce a more favorable ionization state of the key amino acid (Glu-183) and thus reduce radical formation. As a result of higher activity at pH 5-6, the total turnover numbers (TTN, defined as the amount of product produced over the catalytic lifetime of the enzyme) for the oxidation of toluene and o-, m-, p-xylenes in substrate/aqueous emulsion systems ranged from ca. 10% to 110% higher at pH 5.5 (20,000 to 45,000 mol product/mol enzyme) compared to pH 4.1. Furthermore, TTNs of CPO increased with increasing turnover frequencies, indicating that higher activity toward reducing substrates reduces radical formation and stabilizes CPO toward inactivation by H(2)O(2). These findings demonstrate the important relationship between CPO stability and activity, and illustrate that large improvements in CPO activity and stability can be achieved through solvent engineering.

Electronic tuning of β-diketiminate ligands with fluorinated substituents: effects on the O2-reactivity of mononuclear Cu(i) complexes

Copper(i) complexes with the beta-diketiminate ligands HC{C(R)N(Dipp)}{C(R')N(Dipp)}(-) (Dipp = C(6)H(3)(i)Pr(2-)2,6; L(1), R = CF(3), R' = CH(3); L(2), R = R' = CF(3)) have been isolated and fully characterized. On the basis of X-ray structural comparisons with the previously reported complex LCu(CH(3)CN) (L = HC{C(CH(3))N(Dipp)}(2)(-)), the ligand environments at the copper centers in the analogous nitrile adducts with L(1) and L(2) impose similar steric demands. L(1)Cu(CH(3)CN) reacts instantaneously at low temperature with O(2) to form a thermally-unstable intermediate with an isotope-sensitive vibration at 977 cm(-1) (928 cm(-1) with (18)O(2)), in accord with the peroxo O-O stretch associated with side-on coordination for LCu(O(2)). However, L(2)Cu(CH(3)CN) is unreactive toward O(2) even at room temperature. Evaluation of the redox potentials of the nitrile adducts and the CO stretching frequencies of the carbon monoxide adducts revealed an incremental adjustment of the electronic environment at the copper center that correlated with the extent of ligand fluorination. Furthermore, theoretical calculations (DFT, CASPT2) predicted that an increasing extent of Cu(ii)-superoxo character and end-on coordination of the O(2) moiety in the Cu/O(2) product (L(2) > L(1) > L) are accompanied by increases in the free energy for the oxygenation reaction, with L(2) unable to support a Cu/O(2) intermediate. Calculations also predict the 1 : 1 Cu/O(2) adducts to be unreactive with respect to hydrogen atom abstraction from hydrocarbon substrates on the basis of their stability towards both reduction and protonation.

Bacterial Community Changes with N′- N′ Dimethylforamide (DMF) Additives during Polycyclic Aromatic Hydrocarbons (PAH) Biodegardation

This study examined the changes in the bacterial community during biodegradation of polycyclic aromatic hydrocarbon (PAH) substrate when N′-N′ dimethylformamide (DMF) was added. The microbial populations that biodegrade the PAH substrate were assessed by Fluorescence in-situ hybridization (FISH) and changed from 49.45% Archaea and 49.15% Bacteria to 42.00% Archaea and 51.78% Bacteria when the PAH was supplemented with DMF. Nine microorganisms were classified as Gram-negative α-, β- and γ-Proteobacteria bacteria during biodegradation of PAH alone by the Biolog system. Incentive eleven microorganisms obtained from the PAH-DMF mixed substrate were found to be β-, γ-Proteobacteria bacteria, high G+C Gram-positive bacteria (HGC), low G+C Gram-positive bacteria (LGC) and there was even one Deinococcus-Thermus strain; this indicates greater biodiversity. The numbers in the Pseudomonad group were as high as 105-106 CFU ml−1, suggesting that this group plays an important role in PAH biodegradation. Community-Level Physiological Profiling (CLPP) and physiological characterization were different in the PAH biodegradation process with and without DMF. Utilization of the 95 carbon sources from the Biolog GN2 microtiter plate was greater during PAH biodegradation when PAH is present alone compared to that in the presence of DMF. The range of enzymatic activities during PAH biodegradation was lower in the presence of DMF. These results show that DMF should be used with caution when PAH is a substrate during laboratory or pilot biotreatability studies.

Mechanism and selectivity of 2,3-dimethyl-2,3-diphenylbutane mediated addition of vinyltriethoxysilane to polyethylene

The thermolysis of 2,3-dimethyl-2,3-diphenylbutane (bicumene) at temperatures ranging from 220 to 310 °C is used to initiate the radical-mediated graft addition of vinyltriethoxysilane (VTEOS) to polyethylene. Model hydrocarbon studies indicate that the cumyl radicals generated by the slow decomposition of bicumene are capable of direct hydrogen atom abstraction at levels that are sufficient to sustain a graft propagation sequence of high kinetic chain length. The interaction of O 2 with cumyl radicals can lead to oxidation of the initiator and the hydrocarbon substrate, thereby enhancing the macroradical population and improving grafting rates and yields. In addition to providing remarkable kinetic chain lengths for VTEOS additions, high-temperature bicumene-based processes can induce HDPE and LDPE fragmentation such that the effects of radical combination on melt viscosity are counteracted. As a result, alkoxysilane-modified polymers that moisture-cure efficiently can be produced without incurring the undesirable increases in molecular weight that accompany conventional grafting processes.

Cloning and Functional Expression of cDNA Encoding Pheromone Δ9 Acyl‐CoA Desaturase of the Tobacco Cutworm, Spodoptera litura (Lepidoptera: Noctuidae)

ABSTRACT A cDNA encoding pheromone Δ9 acyl‐CoA desaturase, Slit KPSE was isolated from sex pheromone gland of the tobacco cutworm, Spodoptera litura which uses a diene unsaturated fatty acid (UFA) derivative, Z9E11‐14 : 2 as a major pheromone component. The fulllength open reading frame coding region of Slit KPSE was inserted in a yeast shuttle vector, YEpOLEX, and two kinds of yeast (Saccharomyces cerevisiae) mutant strains were transformed with the recombinant vector. In the desaturase‐deficient ole1 strain, Slit KPSE expressed a complementary enzyme producing two kinds of diene UFAs, more 9–16 : 1 and less 9–18 : 1 at a ratio of 1 : 0.74 exhibiting a typical functional characteristics as one of the pheromone Δ9 acyl‐CoA desaturase lineage group, KPSE, but no Δ9 14C monoene was detectable because of too small amount of 14C saturated fatty acid precursor to be reliably used by Slit KPSE in the transformed cells. However, the another transformed yeast strain elo1 which is deficient of elongase 1, an enzyme converting 14C to 16C hydrocarbon substrate, was supplemented with some myristic acid (14 : 0) in the medium, and produced a significant amount of 9–14 : 1 in due to a much enhanced level of the 14C substrate suggesting that Slit KPSE may be responsible for making the Δ9 double bond on the diene pheromone component.

The Leeuwenhoek Lecture 2000 the natural and unnatural history of methane-oxidizing bacteria.

Methane gas is produced from many natural and anthropogenic sources. As such, methane gas plays a significant role in the Earth's climate, being 25 times more effective as a greenhouse gas than carbon dioxide. As with nearly all other naturally produced organic molecules on Earth, there are also micro-organisms capable of using methane as their sole source of carbon and energy. The microbes responsible (methanotrophs) are ubiquitous and, for the most part, aerobic. Although anaerobic methanotrophs are believed to exist, so far, none have been isolated in pure culture. Methanotrophs have been known to exist for over 100 years; however, it is only in the last 30 years that we have begun to understand their physiology and biochemistry. Their unique ability to use methane for growth is attributed to the presence of a multicomponent enzyme system-methane monooxygenase (MMO)-which has two distinct forms: soluble (sMMO) and membrane-associated (pMMO); however, both convert methane into the readily assimilable product, methanol. Our understanding of how bacteria are capable of effecting one of the most difficult reactions in chemistry-namely, the controlled oxidation of methane to methanol-has been made possible by the isolation, in pure form, of the enzyme components.The mechanism by which methane is activated by sMMO involves abstraction of a hydrogen atom from methane by a high-valence iron species (FeIV or possibly FeV) in the hydroxylase component of the MMO complex to form a methyl radical. The radical combines with a captive oxygen atom from dioxygen to form the reaction product, methanol, which is further metabolized by the cell to produce multicarbon intermediates. Regulation of the sMMO system relies on the remarkable properties of an effector protein, protein B. This protein is capable of facilitating component interactions in the presence of substrate, modifying the redox potential of the diiron species at the active site. These interactions permit access of substrates to the hydroxylase, coupling electron transfer by the reductase with substrate oxidation and affecting the rate and regioselectivity of the overall reaction. The membrane-associated form is less well researched than the soluble enzyme, but is known to contain copper at the active site and probably iron. From an applied perspective, methanotrophs have enjoyed variable successes. Whole cells have been used as a source of single-cell protein (SCP) since the 1970s, and although most plants have been mothballed, there is still one currently in production. Our earlier observations that sMMO was capable of inserting an oxygen atom from dioxygen into a wide variety of hydrocarbon (and some non-hydrocarbon) substrates has been exploited to either produce value added products (e.g. epoxypropane from propene), or in the bioremediation of pollutants such as chlorinated hydrocarbons. Because we have shown that it is now possible to drive the reaction using electricity instead of expensive chemicals, there is promise that the system could be exploited as a sensor for any of the substrates of the enzyme.

Peroxide-initiated grafting of maleimides onto hydrocarbon substrates

The grafting of N-phenethyl-maleimide ( 1) onto squalane and eicosane was investigated. As reference substances for spectroscopical investigations homopolymer, N-phenethyl-succinimide ( 2), t-butyl-( 4) and cyclohexyl- N-phenethyl-succinimide ( 6) were synthesized. The grafting reactions were carried out at 150 °C in 1,2-dichlorobenzene with Luperox 130 as initiator (molar ratio hydrocarbon substrate: 1:initiator = 10:1:0.2). Two fractions of graft products were isolated and analysed by 1H NMR, 13C NMR, FTIR and UV spectroscopy, SEC and MALDI-TOF MS to determine the average number of grafted residues per substrate molecule and to elucidate the structure of the grafts and the grafting sites. Overall grafting yields were found to be >90%. Only a small percentage of the total amount of substrate was grafted (2–3%). First fraction of both oligomers (approx. 25 wt%) showed to be a mixture of homopolymers (average degree of polymerization 6) and graft products (approx. 1:3), the latter containing mainly long-chain grafts with an average chain length of 7. The major fraction of graft products contained predominantly single units. As an average number of units per substrate molecule very similar results were obtained for eicosane and squalane ( n = ∼ 3). In the case of squalane single units were found to be linked mainly to tertiary carbon atoms, long chain grafts mainly to secondary C-atoms. Apart from the homopolymers resulting from radical transfer, homopolymers terminated with methyl groups resulting from secondary radicals formed by the decomposition of Luperox were also observed. Homopolymers as well as graft products were found to contain small amounts of maleimide groups. The results suggest that as in the mechanism proposed for maleic anhydride, both inter- and intramolecular hydrogen abstraction occurs as part of the chain process. Termination proceeds mainly by hydrogen transfer and also by disproportionation, to a lesser extent. The formation of long chain grafts on tertiary carbons seems to be sterically hindered.

C−H Activation by a Mononuclear Manganese(III) Hydroxide Complex: Synthesis and Characterization of a Manganese-Lipoxygenase Mimic?

Lipoxygenases are mononuclear non-heme metalloenzymes that regio- and stereospecifically convert 1,4-pentadiene subunit-containing fatty acids into alkyl peroxides. The rate-determining step is generally accepted to be hydrogen atom abstraction from the pentadiene subunit of the substrate by an active metal(III)-hydroxide species to give a metal(II)-water species and an organic radical. All known plant and animal lipoxygenases contain iron as the active metal; recently, however, manganese was found to be the active metal in a fungal lipoxygenase. Reported here are the synthesis and characterization of a mononuclear Mn(III) complex, [Mn(III)(PY5)(OH)](CF(3)SO(3))(2) (PY5 = 2,6-bis(bis(2-pyridyl)methoxymethane)pyridine), that reacts with hydrocarbon substrates in a manner most consistent with hydrogen atom abstraction and provides chemical precedence for the proposed reaction mechanism. The neutral penta-pyridyl ligation of PY5 endows a strong Lewis acidic character to the metal center allowing the Mn(III) compound to perform this oxidation chemistry. Thermodynamic analysis of [Mn(III)(PY5)(OH)](2+) and the reduced product, [Mn(II)(PY5)(H(2)O)](2+), estimates the strength of the O-H bond in the metal-bound water in the Mn(II) complex to be 82 (+/-2) kcal mol(-)(1), slightly less than that of the O-H bond in the related reduced iron complex, [Fe(II)(PY5)(MeOH)](2+). [Mn(III)(PY5)(OH)](2+) reacts with hydrocarbon substrates at rates comparable to those of the analogous [Fe(III)(PY5)(OMe)](2+) at 323 K. The crystal structure of [Mn(III)(PY5)(OH)](2+) displays Jahn-Teller distortions that are absent in [Mn(II)(PY5)(H(2)O)](2+), notably a compression along the Mn(III)-OH axis. Consequently, a large internal structural reorganization is anticipated for hydrogen atom transfer, which may be correlated to the lessened dependence of the rate of substrate oxidation on the substrate bond dissociation energy as compared to other metal complexes. The results presented here suggest that manganese is a viable metal for lipoxygenase activity and that, with similar coordination spheres, iron and manganese can oxidize substrates through a similar mechanism.

Catalytic Allylic Amination versus Allylic Oxidation: A Mechanistic Dichotomy

Allylic oxidation of hydrocarbon substrates is the foundation of many industrial and fine-chemical production processes. Direct allylic oxidation of cycloalkenes (C5-8) has been widely discussed in the chemical literature. However, certain mechanistic details related to the presence of allylic free radicals have yet to be fully resolved. The corresponding copper-catalyzed allylic amination reaction has not been previously achieved. We report the first examples of this class of amination reaction using saccharin and bis-p-toluenesulfonamide as nitrogen sources and t-BuOOH and PhI(saccharinate)2 as oxidants. Kinetic studies on stoichiometric model reactions demonstrate that the oxidant is not involved in the RDS of the transformation, and studies with 3,3,6,6-tetradeuteriocyclohexene conclusively show a mechanistic dichotomy between the catalytic oxidation and amination reactions. Both oxidative processes involve η1-allyl intermediates, and regiochemical results are a consequence of discrete copper complexes. A mechanistic rationale involving allylic transpositions explains this mechanism dichotomy.

Use of claydite-immobilized oil-oxidizing microbial cells for purification of water from oil

Oil-oxidizing bacteria were isolated from oil-polluted soil and water samples and identified as Acinetobacter calcoaceticus K-4, Nocardia vaceinii K-8, Rhodococcus erythropolis EK-1, and Mycobacterium sp. K-2. It was found that immobilization of the bacteria on an expanded clay aggregate accelerated their growth and consumption of hydrocarbon substrates. It was also found that water polluted with 100 mg/l oil could be purified with Rhodococcus erythropolis EK-1 and Nocardia vaceinii K-8 cells immobilized in this way. The dependence of the degree of water purification on its flow rate, aeration, and availability of nitrogen and phosphorus sources was determined. The efficiency of water purification from oil by immobilized Rhodococcus erythropolis EK-1 cells at high flow rates (of up to 0.68 l/h), low aeration (of 0.1 l/l per min) and an intermittent supply of 0.01% diammonium phosphate reached 99.5-99.8%.