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PubMed2003

Towards large-scale synthetic applications of Baeyer-Villiger monooxygenases.

Biocatalysis is coming of age, with an increasing number of reactions being scaled-up and developed. The diversity of reactions is also increasing and oxidation reactions have recently been considered for scale-up to commercial processes. One important chemical conversion, which is difficult to achieve enantio- or enantiotopo- selectively, is the Baeyer-Villiger (BV) oxidation of ketones. Using cyclohexanone monooxygenase to catalyse the reaction produces optically pure esters and lactones with exquisite enantiomeric excess values. Recently, these enzymes and their many applications in synthetic chemistry have been explored. The scale-up of these conversions has been examined with the idea of implementing the first commercial Baeyer-Villiger monooxygenase-based process. Here, we review the state-of-the-art situation for the scale-up and exploitation of these enzymes.

Bioreactors↗
PubMed2004

Stereoselective effects of ketamine on dopamine, serotonin and noradrenaline release and uptake in rat brain slices.

Ketamine (2-(2-chlorophenyl)-(1-methylamino)-cyclohexanone) is a rapid-acting dissociative general anaesthetic whose hallucinogenic properties have made it a popular drug of abuse. Ketamine comprises two optical isomers, with differing pharmacology. In the present study, the effects of (+)- and (-)-ketamine on stimulated efflux and reuptake of dopamine (DA), noradrenaline (NA) and serotonin (5-HT) were compared in isolated superfused slices of the rat caudatoputamen (CPu), ventral bed nucleus of the stria terminalis (BSTV) or dorsal raphe nucleus (DRN), respectively. Monoamine efflux was elicited by local electrical stimulation (20 pulses, 100 Hz trains) at tungsten microelectrodes and measured at adjacent carbon fibre microelectrodes using fast cyclic voltammetry (FCV). In CPu (+)-ketamine increased stimulated DA efflux and slowed DA reuptake in a concentration-dependent manner (25-200 microM). At 100 microM (+)-ketamine increased DA efflux by 109+/-20% (mean+/-S.E.M., n=13) of control values after 30 min (P<0.001 versus control) and prolonged uptake half-time (t(1/2)) by 76+/-38% (n=9, P<0.001) of control. In contrast (-)-ketamine (100 microM) had no effect on DA efflux or uptake. In DRN, both isomers (100 microM) increased stimulated 5-HT efflux. (-)-Ketamine had a larger effect (P<0.001), an 88+/-15% increase in 5-HT efflux (n=9) versus 46+/-10% (n=8) for the (+)-isomer. The isomers had similar effects on 5-HT uptake, increasing t(1/2) by approximately 200%. No evidence of stereospecificity was seen in BSTV: both isomers had small effects (+)- and (-)-ketamine (100 microM) increasing NA efflux by 43+/-10% (n=7, P<0.001) and 29+/-8% (n=7, P<0.001), respectively. The isomers also had identical effects on NA uptake, each increasing uptake t(1/2) by approximately 100%. In summary, our data show that the optical isomers of ketamine have strikingly different stereospecificity for the monoamine systems and one might predict, therefore, a different psychotomimetic potential.

Animals↗
PubMedDate not supplied

Inhibition of copper amine oxidases by pyridine-derived aldoximes and ketoximes.

The reactions of pea diamine oxidase (PSAO) and 2-phenylethylamine oxidase from Arthrobacter globiformis (AGAO) with pyridine-derived oximes were studied. Pyridine carbaldoximes and alkyl pyridyl ketoximes act as strong non-competitive inhibitors of the enzymes. The inhibition constants K(i) of these compounds vary between 10(-4) and 10(-5) M, for AGAO and some of the studied oximes were found even micromolar K(i) values. The presence of pyridine moiety in the studied compounds has remarkable influence on the inhibition potency. Elementary oximes lacking the heterocyclic ring, i.e., aliphatic (acetone oxime), alicyclic (cyclohexanone oxime) and aromatic (benzaldoxime), are considerably weaker non-competitive inhibitors (K(i) similar to 10(-3) or 10(-2) M). The position of the pyridine ring substitution by -C(R)=NOH group does not play a significant role for the inhibition potency of the studied oxime compounds. If the pyridine nitrogen is quaternised (in hydroxyiminomethyl-1-methylpyridinium iodides), the compound looses its inhibitory properties. Extended length of alkyl substituents on the ketoxime group of alkyl pyridyl ketoximes increases the K(i) value. The enzyme-bound copper represents one of possible target sites for pyridine-derived oxime inhibitors. The addition of an alkyl pyridyl ketoxime or a pyridine carbaldoxime to a native PSAO sample perturbs the absorption spectrum of the enzyme (by an absorption increase in the region 300-400 nm) that is not observed in the spectrum of reacted PSAO apoenzyme. However, an additional formation of hydrogen bonds with amino acid side-chains at the active site should be considered, namely for 3- and 4-substituted pyridine derivatives.

Amine Oxidase (Copper-Containing)↗
PubMed1982

[Affinity chromatography of NAD(P)+ dehydrogenases dependent on the concentration of NAD(P)+ bound to ketones or aldehydes].

The use of general ligands such as NAD(P)+ for affinity chromatography of dehydrogenase requires elution with pulses of oxidized or reduced cofactor at suitable concentrations. This method of elution can involve considerable effort before ideal eluent conditions are evolved. We report on a new method of immobilized NAD(P)+ modifications which increases the selectivity of the phase and may be of rather wide application. The immobilized NAD(P)+ is modified by addition of a ketone or an aldehyde substrate of the dehydrogenase which must be purified and becomes a very specific ligand of that dehydrogenase. The adduct of immobilized NAD+ and sodium pyruvate absorbs specifically the lactate dehydrogenase, whereas the adduct of immobilized NAD+ and cyclohexanone adsorbs specifically the horse liver alcohol dehydrogenase. Absorbed dehydrogenases are eluted with NaCl gradients.

Aldehydes↗
PubMed2002

Dechlorination of chlorinated phenols by catalyzed and uncatalyzed Fe(0) and Mg(0) particles.

Uncatalyzed, and palladium-catalyzed Fe(0) and Mg(0) systems were examined for their efficiencies of dechlorination of 2.86 mM 4-chlorophenol (4-CP), 2.52 mM 2,6-dichlorophenol (2,6-DCP), 3.03 mM 2,4,6-trichlorophenol (2,4,6-TCP), and 2.48 mM pentachlorophenol (PCP) in 50/50 (v/v) 2-propanol/water under room temperature and pressure conditions. Previous investigators have found that PCP is extremely recalcitrant under these conditions. In this investigation, complete dechlorination of 5.0 ml of 2.48 mM PCP was observed for 1.0 g of 2659 ppm Pd/Mg (20 mesh) after 48 h. The only detectable products were cyclohexanol and cyclohexanone at 25% yield. No other chlorinated or otherwise products were observed by mass spectral analysis. It is hypothesized that volatile low molecular weight species were formed from the Pd/Mg dechlorination of PCP. Under conditions of equal surface area (0.0786 m2), the approximate order of PCP dechlorination power of these systems followed as 2659 ppm Pd/Mg>319 ppm Pd/Mg>Mg approximately 4856 ppm Pd/Fe>Fe. Degradation of the other chlorinated phenols by all metallic systems was more facile than PCP.

Catalysis↗
PubMed2000

Comparison of electron diffraction data from non-linear optically active organic DMABC crystals obtained at 100 and 300 kV

During the recent past, we have synthesized a new class of molecules with intramolecular two-dimensional charge transfer upon excitation. The present report presents such a molecule, 2,6-bis(4-dimethylamino-benzylidene)-cyclohexanone (DMABC), with an unusually high value of the second-order non-linear optical (NLO) coefficients. In order to optimize the macroscopic NLO properties of the compounds, it is necessary to relate their first hyperpolarizability tensors at a molecular level to those at a crystal bulk level. This requires a complete structure determination and refinement. However, the growth of sufficiently large single crystals, which are needed for structural analysis and refinement by X-ray methods, is a time consuming and sometimes impossible task. We have performed a complete structural analysis by electron diffraction combined with simulation methods and with maximum entropy and log likelihood statistics. In order to improve the quantitative analysis, a 300 kV data set using an on-line CCD camera was added and the best attainable R-values were compared with those from 100 kV data using film emulsions. Details regarding the maximum attainable resolution for both data sets are discussed as well as the problems which arise from the limited dynamic range in photographic emulsions as compared to a 14 bit CCD camera. Once the crystal structure was known, quantum-chemical methods were used to calculate non-linear optical susceptibility tensor components and these were related to the macroscopic coefficients of the crystalline quadratic non-linearity tensor. In the present work, both ab initio and semi-empirical quantum-chemical calculations were employed.

Journal Article↗
PubMed2000

Orbital cortex neuronal responses during an odor-based conditioned associative task in rats.

Neuronal activity in the rat orbital cortex during discrimination of various odors [five volatile organic compounds (acetophenone, isoamyl acetate, cyclohexanone, p-cymene and 1,8-cineole), and food- and cosmetic-related odorants (black pepper, cheese, rose and perfume)] and other conditioned sensory stimuli (tones, light and air puff) was recorded and compared with behavioral responses to the same odors (black pepper, cheese, rose and perfume). In a neurophysiological study, the rats were trained to lick a spout that protruded close to its mouth to obtain sucrose or intracranial self-stimulation reward after presentation of conditioned stimuli. Of 150 orbital cortex neurons recorded during the task, 65 responded to one or more types of sensory stimuli. Of these, 73.8% (48/65) responded during presentation of an odor. Although the mean breadth of responsiveness (entropy) of the olfactory neurons based on the responses to five volatile organic compounds and air (control) was rather high (0.795), these stimuli were well discriminated in an odor space resulting from multidimensional scaling using Pearson's correlation coefficients between the stimuli. In a behavioral study, a rat was housed in an equilateral octagonal cage, with free access to food and choice among eight levers, four of which elicited only water (no odor, controls), and four of which elicited both water and one of four odors (black pepper, cheese, rose or perfume). Lever presses for each odor and control were counted. Distributions of these five stimuli (four odors and air) in an odor space derived from the multidimensional scaling using Pearson's correlation coefficients based on behavioral responses were very similar to those based on neuronal responses to the same five stimuli. Furthermore, Pearson's correlation coefficients between the same five stimuli based on the neuronal responses and those based on behavioral responses were significantly correlated. The results demonstrated a pivotal role of the rat orbital cortex in olfactory sensory processing and suggest that the orbital cortex is important in the manifestation of various motivated behaviors of the animals, including odor-guided motivational behaviors (odor preference).

Animal Feed↗
PubMed2003

Further degradation product of hyperforin from Hypericum perforatum (St John's Wort).

Repeated examination of the aerial parts of Hypericum perforatum yielded a new degradation product of hyperforin (1) namely deoxyfurohyperforin A (2), together with the previously identified furohyperforin (3), furoadhyperforin (4), furohyperforin A (5a and 5b), pyrano[7,28-b]hyperforin (6) and 3-methyl-4,6-di(3-methyl-2-butenyl)-2-(2-methyl-1-oxopropyl)-3-(4-methyl-3-pentenyl)-cyclohexanone (7). The antimicrobial activity of the compounds 3, 5a and 5b, 6 and 7 was tested against Staphylococcus aureus, Candida albicans, Bacillus subtilis and Escherichia coli.

Anti-Bacterial Agents↗
PubMed1999

On the use of liquid chromatography with radio- and ultraviolet absorbance detection coupled to mass spectrometry for improved sensitivity and selectivity in determination of specific radioactivity of radiopharmaceuticals.

Pneumatically assisted electrospray mass spectrometry was evaluated as a complementary detection technique to UV absorbance, for determination of specific radioactivity of tracer molecules to be used in positron emission tomography. Tracers labelled with radionuclides having short half-lives can be synthesised with high specific radioactivity. The UV absorbance detection that is commonly used for the determination does not always have the sensitivity required for those analyses. In comparison, mass spectrometry gave improved detection limits in all but one (nicotine) of the 12 compounds studied. The magnitude of this improvement was more than 100-fold for the compounds ketamine (2-methylamino-2-(2-chloro-phenyl)cyclohexanone), SCH-23390 ((R)-(+)-7-chloro-8-hydroxy-1-methyl-1-phenyl-2,3,4,5-tetra-hydro-1H-3-b enzazepine) and N-methyl-piperidylbenzilate. These improved detection limits, specificity, plus the added certainty of product identity provided by mass spectral data demonstrated the value of the mass spectrometer as a complementary detector in the determination of specific radioactivity.

Chromatography, Liquid↗
PubMed2000

Structure elucidation of methylidene malonate 2.1.2 cyclic trimers with mass spectrometry, liquid chromatography and nuclear magnetic resonance investigations.

The anionic polymerization of methylidene malonate 2.1.2. is able to yield four different molecule types. The major product obtained at pH 5.5 corresponds to a trisubstituted cyclohexanone formed by a back-biting reaction. A mixture of four diastereoisomer couples due to the presence of three asymmetric carbon atoms was produced in the same proportion. These results were deduced from mass spectrometry (MS), liquid chromatography MS (LC-MS) and 1H nuclear magnetic resonance (NMR) investigations.

Chromatography, High Pressure Liquid↗
PubMed1998

Free radical formation during ketamine anesthesia in rats: a cautionary note.

Ketamine is a useful anesthetic agent with good analgesic properties; however, when ketamine was used to anesthetize rats for spin trapping studies of alcohol-induced free radicals, liver extracts contained a strong electron paramagnetic resonance (EPR) signal of a novel radical. The same EPR signal was observed in liver extracts when rats which had not received alcohol were anesthetized with ketamine. When ketamine was added to liver microsomes and NADPH, a nitroxide radical derived from ketamine could be detected in organic extracts. When the spin trapping agent POBN was also added, microsomes produced both a ketamine nitroxide radical and a spin adduct. Similar results were obtained during ketamine oxidation by hydrogen peroxide in a tungstate-catalyzed reaction, or in a Fenton reaction system. The data suggest that the secondary amine group of ketamine can be oxidized to a stable nitroxide which produces an EPR spectrum in the absence of a spin trapping agent. The POBN spin adduct detected may be from a carbon-centered radical in the cyclohexanone ring of ketamine. Because several types of radicals can be formed from ketamine, this agent may not be appropriate as an anesthetic for many types of in vivo spin trapping experiments.

Anesthesia, General↗
PubMed1999

N-terminal 4-imidazolidinone prodrugs of Leu-enkephalin: synthesis, chemical and enzymatic stability studies.

Four N-terminal 4-imidazolidinone prodrugs of Leu-enkephalin are prepared and characterized. Their enzymatic and chemical stability are assessed using high-performance liquid chromatography. The prodrug derivatives are shown to degrade stoichiometrically to Leu-enkephalin in phosphate buffer [t1/2 (0.05 M phosphate buffer without KCl): acetone prodrug (II) 930 min; cyclopentanone prodrug (III): 216 min; cyclohexanone prodrug (IV): 432 min; 4-methylcyclohexanone prodrug (V): 792 min]. Furthermore, the prodrugs are shown to afford global stabilization of the Leu-enkephalin molecule towards the enzymes, aminopeptidase N and angiotensin converting enzyme, primarily responsible for degradation of Leu-enkephalin at the blood-brain barrier and in plasma. Therefore, the 4-imidazolidinones, being metabolic stable and bioreversible, may be suitable prodrug candidates for delivery of Leu-enkephalin to important target areas such as the brain, if given intravenously.

Blood-Brain Barrier↗
PubMed1997

The synthesis of (R)-(+)-lipoic acid using a monooxygenase-catalysed biotransformation as the key step.

2-(2-Acetoxyethyl)cyclohexanone (4) was converted into the lactone (-)-(5) regio- and enantioselectively using 2-oxo-delta 3-4,5,5-trimethylcyclopentenyl acetyl-CoA monooxygenase, an NADPH-dependent Baeyer-Villiger monooxygenase from camphor grown Pseudomonas putida NCIMB 10007. The lactone (-)-(5) was converted into (R)-(+)-lipoic acid in six steps. In contrast cyclopentanone monooxygenase, an NADPH-dependent Baeyer-Villiger monooxygenase from cyclopentanol-grown Pseudomonas sp. NCIMB 9872 selectively oxidized the (S)-enantiomer of the ketone (4) giving better access to optically enriched, naturally occurring lipoic acid.

Biotransformation↗
PubMed2003

Preparation of porous cobalt and nickel oxides from corresponding alkoxides using a sonochemical technique and its application as a catalyst in the oxidation of hydrocarbons.

Porous nickel and cobalt oxides were prepared using their alkoxides as inorganic precursors. The stabilization of the mesostructure is especially critical for divalent elements such as Ni and Co, which do not form any network structure, like silicates. The lack of a network-forming multivalent bond is the probable reason why no stable mesoporous oxides have been synthesized for divalent elements yet. Here we have reported our attempt to synthesize porous oxides of Ni and Co. Octadecylamine has been used as the organic structure-directing agent. The product obtained was put under solvent extraction and calcination at various temperatures to remove the surfactant, followed by characterization using XRD, TEM and BET measurements. The FT/IR and thermal analyses (TGA and DSC) were also carried out for supporting information, such as extent of removal of surfactant from the pores of the metal oxide. A relatively better surface area has been obtained for the Co oxide, but in Ni the surface area found is not as good. A possible reason for that has been discussed. The porous (solvent extracted) cobalt oxide has been used as a catalyst in the oxidation reaction of cyclohexane in mild conditions. The catalyst has shown relatively better conversion of cyclohexane into cyclohexanone and cyclohexanol than the nanostructured cobalt oxide catalyst of regular structure.

Journal Article↗
PubMed1997

Ultrasound effects on photochemical reactions, part 1: photochemical reactions of ketones with alkenes.

Ultrasound considerably enhances and simplifies photochemical reaction of cyclohexanone with cyclohexene. The Paterno-Büchi reaction of acetone with ethyl vinyl ether is enhanced by ultrasound and yields a different ratio of cis/trans oxetanes under sonication by comparison with the silent reaction. Sonication appears to affect the first reaction by homogenization of excited intermediates and by quenching the excited triplet state at the second reaction.

Journal Article↗
PubMed2002

Designing membrane electrochemical reactors for oxidoreductase-catalysed synthesis.

The purpose of this work was to design an electrochemical reactor to enhance the high selectivity of enzyme-catalysed processes. In order to develop economically efficient syntheses, the enzymes must be confined in the strict vicinity of the electrode surface. Here the confinement was achieved with a dialysis membrane in a so-called Dialysis-Membrane Electrochemical Reactor (D-MER). Oxidation of glucose into gluconic acid catalysed by glucose oxidase was a first example. The ADH-catalysed reduction of cyclohexanone into cyclohexanol was also tested in a new type of MER. NADH was electrochemically regenerated thanks to mediator (methyl viologen or rhodium complex). The key point in developing electro-enzymatic process is to ensure the perfect fitting of the reactor design to the reactions that are to be processed.

Alcohol Dehydrogenase↗
PubMed2001

Molecular sieve catalysts for the regioselective and shape- selective oxyfunctionalization of alkanes in air.

Framework-substituted, molecular-sieve, aluminophosphate, microporous solids are the centerpieces of a new approach to the aerobic oxyfunctionalization of saturated hydrocarbons. The sieves, and the few percent of the Al(III) sites within them that are replaced by catalytically active, transition-metal ions in high oxidation states (Co(III), Mn(III), Fe(III)), are designed so as to allow free access of oxygen in to and out of the interior of these high-area solids. Certain metal-substituted, molecular sieves permit only end-on approach of linear alkanes to the active centers, thereby favoring enhanced reactivity of the terminal methyl groups. By optimizing cage dimension, with respect to that of the hydrocarbon reactant, as well as adjusting the average separation of active centers within a cage, and by choosing the sieve with the appropriate pore aperture, highly selective conversions such as n-hexane to hexanoic acid or adipic acid, and cyclohexane to cyclohexanol, cyclohexanone, or adipic acid, may be effected at low temperature, heterogeneously in air.

Aerobiosis↗