Electrochemistry of macrocyclic cobalt(III/II) hexaamines: Electrocatalytic hydrogen evolution in aqueous solution

The macrocyclic cobalt hexaamines [Co(trans-diammac)](3+) and [Co(cis-diammac)](3+) (diammac = 6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine) are capable of reducing the overpotential for hydrogen evolution on a mercury cathode in aqueous solution. Protons are reduced in a catalytic process involving reoxidation of the Co-II species to its parent Co-III complex. The cycle is robust at neutral pH with no decomposition of catalyst. The stability of the [Co(trans-diammac)](2+) and [Co(cis-diammac)](2+) complexes depends on the pH of the solution and the coordinating properties of the supporting electrolyte. Electrochemical studies indicate that the adsorbed Co-II complex on the surface of mercury is the active catalyst for the reduction of protons to dihydrogen.

Complexes of 1-thia-4,7,10-triazacyclododecane ([12]aneN(3)S) - Synthesis, structure and stability constants

The 12-membered macrocyclic ligand 1-thia-4,7, 10-triazacyclododecane ([12]aneN(3)S) has been synthesised, although upon crystallization from acetonitrile a product in which carbon dioxide had added to one secondary amine in the macrocyclic ring (H[12]aneN(3)SCO(2). H2O) was isolated and subsequently characterised by X-ray crystallography. The protonation constants for [12]aneN(3)S and stability constants with Zn(II), Pb(II), Cd(II) and Cu(II) have been determined either potentiometrically or spectrophotometrically in aqueous solution, and compared with those measured or reported for the ligands 1-oxa-4,7,10-triazacyclododecane ([12]aneN(3)O) and 1,4,7,10-tetraazacyclododecane ([12]aneN(4)). The magnitudes of the stability constants are consistent with trends observed previously for macrocyclic ligands as secondary amine donors are replaced with oxygen and thioether donors although the stability constant for the [Hg([12]aneN(4))](2+) complex has been estimated from an NMR experiment to be at least three orders of magnitude larger than reported previously. Zinc(II), mercury(II), lead(II), copper(II) and nickel(II) complexes of [12]aneN(3)S have been isolated and characterised by X-ray crystallography. In the case of copper(II), two complexes [Cu([12]aneN(3)S)(H2O)](ClO4)(2) and [Cu-2([12]aneN(3)S)(2)(OH)(2)](ClO4)(2) were isolated, depending on the conditions employed. Molecular mechanics calculations have been employed to investigate the relative metal ion size preferences of the [3333], asym-[2424] and sym-[2424] conformation isomers. The calculations predict that the asym-[2424] conformer is most stable for M-N bond lengths in the range 2.00-2.25 Angstrom whilst for the larger metal ions the [3333] conformer is dominant. The disorder seen in the structure of the [Zn([12]aneN(3)S)(NO3)](+) complex is also explained by the calculations. (C) 1999 Elsevier Science Ltd. All rights reserved.

The Ni-II, Hg-II and Cu-II complexes of 12-membered-ring mixed-donor macrocycles

The structures of diaqua(1,7-dioxa-4-thia-10-azacyclododecane)nickel dinitrate, [Ni(C8H17NO2S)(H2O)(2)](NO3)(2), (I), bis(nitrato-O,O')(1,4,7-trioxa-10-azacyclododecane)mercury, [Hg(NO3)(2)(C8H17NO3)], (II), and aqua(nitrato-O)(1-oxa-4,7,10-triazacyclododecane)copper nitrate, [Cu(NO3)(C8H19N3O)(H2O)]NO3, (III), reveal each macrocycle binding in a tetradentate manner. The conformations of the ligands in (I) and (III) are the same and distinct from that identified for (II). These differences are in agreement with molecular-mechanics predictions of ligand conformation as a function of metal-ion size.

Ni-II and Zn-II complexes of the hexadentate macrocyclic ligand cis-6,13-dimethyl-1,4,8,11-tetraazacyclotetra- decane-6,13-diamine

The title pendent-arm macrocyclic hexaamine ligand binds stereospecifically in a hexadentate manner, and we report here its isomorphous Ni-II and Zn-II complexes (both as perchlorate salts), namely (cis-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine-kappa(6)N)nickel(II) diperchlorate, [Ni(C12H30N6)](ClO4)(2), and (cis-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine-kappa(6)N)zinc(II) diperchlorate, [Zn(C-12 H30N6)](ClO4)(2). Distortion of the N-M-N valence angles from their ideal octahedral values becomes more pronounced with increasing metal-ion size and the present results are compared with other structures of this ligand.

Characterization of the structural and surface properties of chemically modified MCM-41 material

Mesoporous Mobil catalytic materials of number 41 (MCM-41) silica was chemically modified using both inorganic and organic precursors and characterized using the techniques, XRD, XPS, MAS NMR, FTIR, W-Vis, and physical adsorption of nitrogen, hydrocarbons (hexane, benzene, acetone, and methanol) and water vapor. Modification using organic reagents was found to result in a significant loss in porosity and a shape change of surface properties (increased hydrophobicity and decreased acidity). With inorganic modifying reagents, the decrease in porosity was also observed while the surface properties were not significantly altered as reflected by the adsorption isotherms of organics and water vapors. Chemical modifications can greatly improve the hydrothermal stability of MCM-41 material because of the enhanced surface hydrophobicity (with organic modifiers) or increased pore wall thickness (with inorganic modifiers). (C) 2000 Elsevier Science B.V. All rights reserved.

Comprehensive structural characterization of MCM-41: From mesopores to particles

In the present work the meso- and macro-structural characteristics of the mesoporous adsorbent MCM-41 have been estimated with the help of various techniques. The structure is found to comprise four different length scales: that of the mesopores, the crystallites, the grains and of the particles. It was found that the surface area estimated by the use of small angle scattering techniques is higher, while that estimated by mercury porosimetry is much lower, than that obtained from gas adsorption methods. Based on the macropore characterization by mercury porosimetry, and the considerable macropore area determined, it is seen that the actual mesopore area of MCM-41 may be significantly lower than the BET area. TEM studies indicated that MCM-41 does not have an ideal mesopore structure; however, it may still be treated as a model mesoporous material for gas adsorption studies because of the large radius of curvature of the channels.

A dual catalyst bed system for the elimination of hydrogen from CO2 feed gas in urea synthesis

A dual catalyst bed system (Au/Fe2O3 + Pt-Pd/Al2O3) for eliminating hydrogen from the CO2 feed gas in urea synthesis is found to be far superior to commercially available and patented catalysts in catalytic activity. At relatively low temperatures, hydrogen is eliminated and coexistent CO is also oxidized completely to useful CO2. This can avoid effectively the accidental explosion of hydrogen-oxygen-ammonia mixed gases, thus ensuring the safety of urea synthesis.

Copper/MCM-41 as catalyst for the wet oxidation of phenol

A heterogeneous copper catalyst supported on mesoporous MCM-41 was developed. The parent MCM-41 has a large pore area of over 1400 m(2)/g. Copper was chosen as the active element of catalyst and loaded into MCM-41 by adsorption at ambient temperature. The prepared catalysts were evaluated in the catalytic wet oxidation of phenol solution with an initial concentration of 1,300 ppm at 150 and 200 degreesC. The catalyst was found to be of high catalytic activity. It is also shown that the catalyst with a higher copper loading exhibits higher ability of accelerating the catalytic reaction to certain extent but reaches its constant level afterwards. (C) 2001 Elsevier Science B.V. All rights reserved.

Copper/MCM-41 as catalyst for photochemically enhanced oxidation of phenol by hydrogen peroxide

Heterogeneous copper catalyst was developed using the mesoporous molecular sieve MCM-41 as the catalyst support. Copper was impregnated onto the support. Catalysts with different copper loadings were obtained. The performance of the developed catalysts was evaluated in photochemically enhanced oxidation of phenol using hydrogen peroxide as the oxidant. The catalyst was found to significantly increase the oxidation rate and enhance the removal level of phenol with UV light present. The effects of copper loading on the catalyst, photo (UV), H2O2 concentration, and catalyst dosage on the photo-oxidation of phenol were studied. (C) 2001 Elsevier Science B.V. All rights reserved.

Physiological role of calcium-activated potassium currents in the rat lateral amygdala

Principal neurons in the lateral nucleus of the amygdala (LA) exhibit a continuum of firing properties in response to prolonged current injections ranging from those that accommodate fully to those that fire repetitively. In most cells, trains of action potentials are followed by a slow after hyperpolarization (AHP) lasting several seconds. Reducing calcium influx either by lowering concentrations of extracellular calcium or by applying nickel abolished the AHP, confirming it is mediated by calcium influx. Blockade of large conductance calcium-activated potassium channel (BK) channels with paxilline, iberiotoxin, or TEA revealed that BK channels are involved in action potential repolarization but only make a small contribution to the fast AHP that follows action potentials. The fast AHP was, however, markedly reduced by low concentrations of 4-aminopyridine and alpha-dendrotoxin, indicating the involvement of voltage-gated potassium channels in the fast AHP. The medium AHP was blocked by apamin and UCL1848, indicating it was mediated by small conductance calcium-activated potassium channel (SK) channels. Blockade of these channels had no effect on instantaneous firing. However, enhancement of the SK-mediated current by 1-ethyl-2-benzimidazolinone or paxilline increased the early interspike interval, showing that under physiological conditions activation of SK channels is insufficient to control firing frequency. The slow AHP, mediated by non-SK BK channels, was apamin-insensitive but was modulated by carbachol and noradrenaline. Tetanic stimulation of cholinergic afferents to the LA depressed the slow AHP and led to an increase in firing. These results show that BK, SK, and non-BK SK-mediated calcium-activated potassium currents are present in principal LA neurons and play distinct physiological roles.

Directed evolution of mammalian cytochrome P450 enzymes involved in xenobiotic metabolism

Directed evolution of cytochrome P450 enzymes represents an attractive means of generating novel catalysts for specialized applications. Xenobiotic-metabolizing P450s are particularly well suited to this approach due to their inherent wide substrate specificity. In the present study, a novel method for DNA shuffling was developed using an initial restriction enzyme digestion step, followed by elimination of long parental sequences by size-selective filtration. P450 2C forms were subjected to a single round of shuffling then coexpressed with reductase in E. coli. A sample (54 clones) of the resultant library was assessed for sequence diversity, hemo- and apoprotein expression, and activity towards the substrate indole. All mutants showed a different RFLP pattern compared to all parents, suggesting that the library was free from contamination by parental forms. Haemoprotein expression was detectable in 45/54 (83%) of the mutants sampled. Indigo production was less than or comparable to the activities of one or more of the parental P450s, but three mutants showed indirubin production in excess of that seen with any parental form, representing a gain of function. In conclusion, a method is presented for the effective shuffling of P450 sequences to generate diverse libraries of mutant P450s containing a high proportion of correctly folded hemoprotein, and minimal contamination with parental forms.

Oxidation of toluene in waste gas streams using mesoporous Ti-hexagonal mesoporous silica

Various mesoporous catalysts with titanium loadings between 0.5 and 4 Ti wt. % and surface areas between 600 and 1,600 m(2)/g were synthesized using the molecular designed dispersion technique. These catalysts were tested using toluene oxidation in a fixed bed reactor at temperatures between 300 and 550degreesC. The reaction products were found to be CO2 and CO with selectivity towards CO2 above 80% for all catalysts. The catalytic activity of the catalysts increases with titanium loading. The total conversion at 550degreesC was not affected by the textural porosity, but increased textural porosity did significantly reduce the ignition temperature by up to 50degreesC. The Thiele modulus was calculated to be much less than one for all these materials indicating that the reaction rate is not diffusion, limited.

New porphyrins tailored as biodiesel fluorescent markers

This work reports the synthesis, characterization, and evaluation of new porphyrins tailored to become biodiesel fluorescent markers. The compounds were obtained by the synthetic modification of the commercially available porphyrin 5,10,15,20-meso-tetrakis(pentafluorophenyl)porphyrin (TPPF(20)) using ethanol and hexadecan-1-ol (cetylic alcohol) as nucleophilic reagents. The stability of the marked biodiesel fuel solutions was investigated every 15 days for a total period of 3 months, and under different storage temperature and light exposure condition, simulating the conventional stock conditions. The influence of the different substituents of the porphyrins on the fluorescence properties of the biodiesel fuel markers was also assessed. The resulting porphyrins were highly soluble in biodiesel fuel and displayed strong fluorescence characterized by two strong emission bands. The fluorescent markers did not affect the biodiesel physical properties and were stable in storage conditions for at least 3 months at a concentration of 4 ppm. The best storage condition was found to be absence of light and 6 degrees C; the limit of detection by photoluminescence technique had magnitude of 10(-13) mol L(-1). The synthesized porphyrins were characterized by nuclear magnetic resonance ((1)H-NMR and (19)F-NMR), mass spectrometry (HRMS), ultraviolet visible absorption spectroscopy, and photoluminescence spectroscopy. (C) 2011 Elsevier Ltd. All rights reserved.

Application of Ti/RuO(2)-Ta(2)O(5) electrodes in the electrooxidation of ethanol and derivants: Reactivity versus electrocatalytic efficiency

The influence of the preparation method on the performance of RuO(2)-Ta(2)O(5) electrodes was evaluated toward the ethanol oxidation reaction (EOR). Freshly prepared RuO(2)-Ta(2)O(5) thin films containing between 30 and 80 at.% Ru were prepared by two different methods: the modified Pechini-Adams method (DPP) and standard thermal decomposition (STD). Electrochemical investigation of the electrode containing RuO(2)-Ta(2)O(5) thin films was conducted as a function of electrode composition in a 0.5-mol dm(-3) H(2)SO(4) solution, in the presence and absence of ethanol and its derivants (acetaldehyde and acetic acid). At a low ethanol concentration (5 mmol dm(-3)), ethanol oxidation leads to high yields of acetic acid and CO(2). On the other hand, an increase in ethanol concentration (15-1000 mmol dm(-3)) favors acetaldehyde formation, so acetic acid and CO(2) production is hindered, in this case. Electrodes prepared by DPP provide higher current efficiency than STD electrodes for all the investigated ethanol concentrations. This may be explained by the increase in electrode area obtained with the DPP preparation method compared with STD. (c) 2008 Elsevier Ltd. All rights reserved.

Ironporphyrin immobilized onto montmorillonite as a bimimetical model for azo dye oxidation

In this work, we studied the oxidation of the azo dye Disperse orange 3 (DO3) by hydrogen peroxide, catalyzed by 5,10,15, 20-tetrakis(4-N-methylpyridyl)porphyrin iron(III) chloride immobilized onto montmorillonite K10, FeP-K10. Results showed that the FeP-K10/H2O2 system is efficient for discoloration of the DO3 dye, especially at pH 3.0. The catalyst was shown to be relatively stable and could be recycled many times, leading to good yields. DO3 oxidation products were analyzed by gas chromatography and mass spectrometry, being 4-nitroaniline the main product. Tert-butylhydroperoxide and iodosylbenzene were also used as oxidants, giving rise to 4-nitroaniline as product too. The studied system is a good biomimetic model of oxidative enzymes, being a promising discoloring agent for azo dyes. (C) 2007 Elsevier Ltd. All rights reserved.