A first principles study of CH3 dehydrogenation on Ni(111)

Density functional theory with gradient corrections and spin polarization has been used to study the dehydrogenation of CH3 on Ni(111), a crucial step in many important catalytic reactions. The reaction, CH3(ads)--> CH2(ads)+H-(ads), is about 0.5 eV endothermic with an activation energy of more than 1 eV. The overall reaction pathway is rather intriguing. The C moiety translates from a hcp to a fcc site during the course of the reaction. The transition state of the reaction has been identified. The CH3 species is highly distorted, and both C and the active H are centered nearly on top of a row of Ni atoms with a long C-H bond length of 1.80 Angstrom. The local density of states coupled with examination of the real space distribution of individual quantum states has been used to analyze the reaction pathway. (C) 2000 American Institute of Physics. [S0021-9606(00)30218-5].

Moving from Batch to Continuous Operation for the Liquid Phase Dehydrogenation of Tetrahydrocarbazole

Despite the numerous advantages of continuous processing, high-value chemical production is still dominated by batch techniques. In this paper, we investigate options for the continuous dehydrogenation of 1,2,3,4- tetrahydrocarbazole using a trickle bed reactor operating under realistic liquid velocities with and without the addition of a hydrogen acceptor. Here, a commercial 5 wt % Pd/Al₂O₃ catalyst was observed to slowly deactivate, hence proving unsuitable for continuous use. This deactivation was attributed to the strong adsorption of a byproduct on the surface of the support. Application of a base washing technique resolved this issue and a stable continuous reaction has been demonstrated. As was previously shown for the batch reaction, the addition of a hydrogen acceptor gas (propene) can increase the overall catalytic activity of the system. 

Elucidating the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts: A density functional theory study

Abstract The dehydrogenation of cyclohexanol to cyclohexanone is very important in the manufacture of nylon. Copper-based catalysts are the most popular catalysts for this reaction, and on these catalysts the reaction mechanism and active site are in debate. In order to elucidate the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts, density functional theory with dispersion corrections were performed on up to six facets of copper in two different oxidation states: monovalent copper and metallic copper. By calculating the surface energies of these facets, Cu(111) and Cu2O(111) were found to be the most stable facets for metallic copper and for monovalent copper, respectively. On these two facets, all the possible elementary steps in the dehydrogenation pathway of cyclohexanol were calculated, including the adsorption, dehydrogenation, hydrogen coupling and desorption. Two different reaction pathways for dehydrogenation were considered on both surfaces. It was revealed that the dehydrogenation mechanisms are different on these two surfaces: on Cu(111) the hydrogen belonging to the hydroxyl is removed first, then the hydrogen belonging to the carbon is subtracted, while on Cu2O(111) the hydrogen belonging to the carbon is removed followed by the subtraction of the hydrogen in the hydroxyl group. Furthermore, by comparing the energy profiles of these two surfaces, Cu2O(111) was found to be more active for cyclohexanol dehydrogenation than Cu(111). In addition, we found that the coordinatively unsaturated copper sites on Cu2O(111) are the reaction sites for all the steps. Therefore, the coordinatively unsaturated copper site on Cu2O(111) is likely to be the active site for cyclohexanol dehydrogenation on the copper-based catalysts.

Biotransformation of Substituted Pyridines with Dioxygenase-containing Microorganisms.

A series of 2-, 3- and 4-substituted pyridines was metabolised using the mutant soil bacterium Pseudomonas putida UV4 which contains a toluene dioxygenase (TDO) enzyme. The regioselectivity of the biotransformation in each case was determined by the position of the substituent. 4-Alkylpyridines were hydroxylated exclusively on the ring to give the corresponding 4-substituted 3-hydroxypyridines, while 3-alkylpyridines were hydroxylated stereoselectively on C-1 of the alkyl group with no evidence of ring hydroxylation. 2-Alkylpyridines gave both ring and side-chain hydroxylation products. Choro- and bromo-substituted pyridines, and pyridine itself, while being poor substrates for P. putida UV4, were converted to some extent to the corresponding 3-hydroxypyridines. These unoptimised biotransformations are rare examples of the direct enzyme-catalysed oxidation of pyridine rings and provide a novel synthetic method for the preparation of substituted pyridinols. Evidence for the involvement of the same TDO enzyme in both ring and side-chain hydroxylation pathways was obtained using a recombinant strain of Escherichia coli (pKST11) containing a cloned gene for TDO. The observed stereoselectivity of the side-chain hydroxylation process in P. putida UV4 was complicated by the action of an alcohol dehydrogenase enzyme in the organism which slowly leads to epimerisation of the initial (R)-alcohol bioproducts by dehydrogenation to the corresponding ketones followed by stereoselective reduction to the (S)-alcohols.

A comparative study of the synthesis of 3-substituted catechols using an enzymatic and a chemoenzymatic method

A series of cis-dihydrodiol metabolites, available from the bacterial dioxygenase-catalysed oxidation of monosubstituted benzene substrates using Pseudomonas putida UV4, have been converted to the corresponding catechols using both a heterogeneous catalyst (Pd/C) and a naphthalene cis-diol dehydrogenase enzyme present in whole cells of the recombinant strain Escherichia coli DH5 alpha(pUC129: nar B). A comparative study of the merits of both routes to 3-substituted catechols has been carried out and the two methods have been found to be complementary. A similarity in mechanism for catechol formation under both enzymatic and chemoenzymatic conditions, involving regioselective oxidation of the hydroxyl group at C-1, has been found using deuterium labelled toluene cis-dihydrodiols. The potential, of combining a biocatalytic step (dioxygenase-catalysed cis-dihydroxylation) with a chemocatalytic step (Pd/C-catalysed dehydrogenation), into a one-pot route to catechols, from the parent substituted benzene substrates, has been realised.

A structural and electrochemical investigation of 1-alkyl-3-methylimidazollum salts of the nitratodioxouranate(VI) anions [{UO2(NO3)(2)}(2)(mu(4)-C2O4)](2-), [UO2(NO3)(3)](-), and [UO2(NO3)(4)](2-)

The properties of the 1-butyl-3-methylimidazolium salt of the dinuclear mu(4)-(O,O,O',O'-ethane-1,2-dioato)bis[bis-(nitrato-O,O)dioxouranate(VI)] anion have been investigated using electrochemistry, single-crystal X-ray crystallography, and extended X-ray absorbance fine structure spectroscopy: the anion structures from these last two techniques are in excellent agreement with each other. Electrochemical reduction of the complex leads to the a two-electron metal-centered reduction of U(VI) to U(IV), and the production Of UO2, or a complex containing UO2. Under normal conditions, this leads to the coating of the electrode with a passivating film. The presence of volatile organic compounds in the ionic liquids 1-alkyl-3-methylimidazolium nitrate (where the 1-alkyl chain was methyl, ethyl, propyl, butyl, pentyl, hexyl, dodecyl, hexadecyl, or octadecyl) during the oxidative dissolution of uranium(IV) oxide led to the formation of a yellow precipitate. To understand the effect of the cation upon the composition and structure of the precipitates, 1-alkyl-3-methylimidazolium salts of a number of nitratodioxouranate(VI) complexes were synthesized and then analyzed using X-ray crystallography. It was demonstrated that the length of the 1-alkyl chain played an important role, not only in the composition of the complex salt, but also in the synthesis of dinuclear anions containing the bridging mu(4)-(O,O,O',O'-ethane-1,2-dioato), or oxalato, ligand, by protecting it from further oxidation.

An EXAFS, X-ray diffraction, and electrochemical investigation of 1-alkyl-3-methylimidazolium salts of [{UO2(NO3)(2)}(2)(mu(4)-C2O4)](2-)

The structure of the 1-alkyl-3-methylimidazolium salts of the dinuclear mu(4)-(O,O,O',O'-ethane-1,2-dioato)-bis[bis(nitrato-O,O)dioxouranate(VI)] anion have been investigated using single crystal X-ray crystallography. In addition, EXAFS and electrochemical studies have been performed on the [C(4)mim](+) salt which is formed following the oxidative dissolution of uranium(IV) oxide in [C(4)mim][NO3]. EXAFS analysis of the solution following UO2 dissolution indicates a mixture of uranyl nitrate and mu(4)-(O,O,O',O'-ethane-1,2-dioato)-bis[bis(nitrato-O,O)dioxouranate(VI)] anions are formed.

The possibility of single C-H bond activation in CH4 on a MoO3-supported Pt catalyst: A density functional theory study

Methane activation is a crucial step in the conversion of methane to valuable oxygenated products. In heterogeneous catalysis, however, methane activation often leads to complete dissociation: If a catalyst can activate the first C-H bond in CH4, it can often break the remaining C-H bonds. In this study, using density functional theory, we illustrate that single C-H bond activation in CH4 is possible. We choose a model system which consists of isolated Pt atoms on a MoO3(010) surface. We find that the Pt atoms on this surface can readily activate the first C-H bond in methane. The reaction barrier of only 0.3 eV obtained in this study is significantly lower than that on a Pt(111) surface. We also find, in contrast to the processes on pure metal surfaces, that the further dehydrogenation of methyl (CH3) is very energetically unfavorable on the MoO3-supported Pt catalyst. (C) 2002 American Institute of Physics.

Enzymatic and chemoenzymatic synthesis of arene trans-dihydrodiols

Several potential approaches to the enzyme-catalysed synthesis of arene trans-diols have been examined including epoxidation/hydrolysis, bis-benzylic hydroxylation, cis-dihydroxylation/alcohol dehydrogenation/ketone reduction, cisdihydroxylation/cis-trans isomerisation. and multi-enzyme synthesis of trans-dihydrodiol secondary metabolites from primary metabolites. The lack of general applicability of these enzymatic methods has led to the development of several chemoenzymatic routes for the synthesis of a series of trans-dihydrodiols from the readily available cis-dihydrodiol precursors. Partial hydrogenation of cis-dihydrodiol metabolites to yield the corresponding cis-tetrahydrodiols followed by a regioselective Mitsunobu inversion process gave trans-tetrahydrodiols that were in turn converted to trans-dihydrodiols. The formation of anti-benzene dioxides or iron tricarbonyl complexes from the corresponding cis-dihydrodiol precursors provided shorter and more convenient chemoenzymatic routes to trans-dihydrodiols. The application of cis-dihydrodiol metabolites of polycyclic azaarenes in the synthesis of the corresponding arene oxides followed by chemical hydrolysis provides a convenient route to trans-dihydrodiols. (C) 2002 Elsevier Science B.V. All rights reserved.

Hydroisomerisation of n-alkanes over partially reduced MoO3: Promotion by CoAlPO-11 and relations to reaction mechanism and rate-determining step

The reaction mechanism and the rate-determining step (RDS) of the isomerisation of n-alkanes (C-4-C-6) over partially reduced MoO3 catalysts were studied through the effects of the addition of an alkene isomerisation catalyst (i.e. CoAlPO- 11). When an acidic CoAlPO- 11 sample was mechanically mixed with the MoO3, a decrease of the induction period and an increase of the steady-state conversion of n-butane to isobutane were observed. These data support previous assumptions that a bifunctional mechanism occurred over the partially reduced MoO3 (a complex nanoscale mixture of oxide-based phases) during n-butane isomerisation and that the RDS was the skeletal isomerisation of the linear butene intermediates. The only promotional effect of CoAlPO-11 on the activity of partially reduced MoO3 for C-5-C-6 alkane hydroisomerisation was a reduction of the induction period, as the RDS at steady-state conditions appeared to be dehydrogenation of the alkane in this case. However, lower yields of branched isomers were observed in this case, the reason of which is yet unclear. (c) 2005 Elsevier B.V. All rights reserved.

VEGF-induced retinal angiogenic signalling is critically dependent on Ca2+ signalling via Ca2+/calmodulin-dependent protein kinase II

Purpose. The authors conducted an in vitro investigation of the role of Ca2+-dependent signaling in vascular endothelial growth factor (VEGF)-induced angiogenesis in the retina.

Methods. Bovine retinal endothelial cells (BRECs) were stimulated with VEGF in the presence or absence of 1,2-bis(2-aminophenoxy)ethane-N,N,N',N'-tetraacetic acid-acetoxymethyl ester (BAPTA-AM; intracellular Ca2+ chelator), U73122 (phospholipase C (PLC) inhibitor), xestospongin C (Xe-C), and 2-aminoethoxydiphenyl borate (2APB) (inhibitors of inositol-1,4,5 triphosphate (IP3) signaling). Intracellular Ca2+ concentration ([Ca2+]i) was estimated using fura-2 Ca2+ microfluorometry, Akt phosphorylation quantified by Western blot analysis, and angiogenic responses assessed using cell migration, proliferation, tubulogenesis, and sprout formation assays. The effects of the Ca2+/calmodulin-dependent protein kinase II (CaMKII) inhibitor KN93 were also evaluated on VEGF-induced Akt signaling and angiogenic activity.

Results. Stimulation of BRECs with 25 ng/mL VEGF induced a biphasic increase in [Ca2+]i, with an initial transient peak followed by a sustained plateau phase. VEGF-induced [Ca2+]i increases were almost completely abolished by pretreating the cells with BAPTA-AM, U73122, Xe-C, or 2APB. These agents also inhibited VEGF-induced phosphorylation of Akt, cell migration, proliferation, tubulogenesis, and sprouting angiogenesis. KN93 was similarly effective at blocking the VEGF-induced activation of Akt and angiogenic responses.

Conclusions. VEGF increases [Ca2+]i in BRECs through activation of the PLC-IP3 signal transduction pathway. VEGF-induced phosphorylation of the proangiogenic protein Akt is critically dependent on this increase in [Ca2+]i and the subsequent activation of CaMKII. Pharmacologic inhibition of Ca2+-mediated signaling in retinal endothelial cells blocks VEGF-induced angiogenic responses. These results suggest that the PLC/IP3/Ca2+/CaMKII signaling pathway may be a rational target for the treatment of angiogenesis-related disorders of the eye.

Influence of Sous Vide and Water Immersion Processing on Polyacetylene Content and Instrumental Color of Parsnip (Pastinaca sativa) Disks

The effect of blanching (95 ± 3 °C) followed by sous vide (SV) processing (90 °C for 10 min) on levels of two polyacetylenes in parsnip disks immediately after processing and during chill storage was studied and compared with the effect of water immersion (WI) processing (70 °C for 2 min.). Blanching had the greatest influence on the retention of polyacetylenes in sous vide processed parsnip disks resulting in significant decreases of 24.5 and 24% of falcarinol (1) and falcarindiol (2) respectively (p < 0.05). Subsequent SV processing did not result in additional significant losses in polyacetylenes compared to blanched samples. Subsequent anaerobic storage of SV processed samples resulted in a significant decrease in 1 levels (p < 0.05) although no change in 2 levels was observed (p > 0.05). 1 levels in WI processed samples were significantly higher than in SV samples (p = 0.05). 2 was particularly susceptible to aerobic storage following WI processing with losses of up to 70% occurring after 5 days storage. 1 type polyacetylene undergoes degradation such as oxidation, dehydrogenation when thermally treated forming oxidized form of 1 type molecules, in this case falcarindione, dehydrofalcarinol, dehydrofalcarinone. Thermal processing had a significant effect on instrumental color of parsnip samples compared to minimally processed in both SV and WI processed samples resulting in parsnip disks becoming darker, yellower and browner following processing and storage.

Pretreatment Effect on Pt/CeO2 Catalyst in the Selective Hydrodechlorination of Trichloroethylene

Pt-ceria catalysts present different surface chemistries depending on the preparation method and the pretreatment. The catalytic behavior of Pt/CeO2 catalysts in the hydrodechlorination of trichloroethylene (TCE) to ethylene was examined as a function of the pretreatment conditions and the noble metal precursor salts. Using FTIR and X-ray photoelectron spectroscopy, significant differences were observed in the surface properties of Pt/CeO2 prepared from the H2PtCl6 precursor after different pretreatment procedures (i.e.. reduction or oxidation-reduction). These surface changes are related to chloride residues from the synthesis. Strong changes were observed in the selectivity of the catalysts to ethylene depending on the pretreatment conditions. The 0.5%Pt/CeO2 catalyst showed a 13% selectivity toward ethylene after reduction, whereas alter oxidation, followed by reduction, the selectivity increased up to 85% at the same conversion level. This effect was only observed when a chloride-containing precursor was used in the preparation. In this way, it is demonstrated that the use of a Cl-containing Pt precursor and an air treatment prior to reduction strongly improves the ethylene selectivity of Pt-CeO2 dechlorination catalysts. This can be explained by formation or a CeOCl phase during the synthesis that decomposes upon air tempering, producing oxygen vacancies on the ceria support. We propose that these oxygen vacancies are active for cleaving off Cl from the TCE. Pt then supplies II to clean-off Cl as HCl. Reaction of TCE on Pt produces rather ethane, so Pt may be partly Cl-poisoned for the hydrodechlorination reaction but not for II, dissociation or CO adsorption.

Structural and kinetic studies of spin crossover in an Iron(II) complex with a novel tripodal ligand

Configurational and ligand conformational influences on the kinetics of (1)A(1) reversible arrow T-5(2) spin crossover in the Fe(II) complex with the novel tripodal ligand, 1,1,1-tris((N-(2-pyridylmethyl)-N-methylamino)methyl)ethane (tptMetame), have been explored. Despite having six chelate rings and three chiral nitrogen atoms, only one enantiomeric pair of isomers, Delta, SSS, and Lambda, RRR, of the complex ion is observed. The conformation of the three rings forming the upper ''cap'' of the complex structure can be assigned delta or lambda with respect to the 3-fold molecular axis. X-ray data at 300 and 153 K, above and below the critical temperature for the spin transition, show that the conformation of the ligand ''cap'' is the same as the absolute configuration of the complex, with the same Lambda lambda(CAP)(or Delta delta(CAP)) combination prevailing for both the LS ((1)A(1)) and HS (T-5(2)) isomers. Molecular mechanics calculations further show that the ligand energy remains lowest for this Lambda lambda(CAP) (or Delta delta(CAP)) combination at all Fe-N distances over the range spanning the LS and HS isomers. Measurements of the spin crossover relaxation time have been carried out in solution over the temperature range 293-170 K. The observed monophasic relaxation traces are also consistent with the absolute configuration of the complex remaining unaltered during the spin crossover.