Investigating the mechanism of the H 2-assisted selective catalytic reduction (SCR) of NOx with octane using fast cycling transient in situ DRIFTS-MS analysis

A mechanistic study of the H-2-assisted Selective Catalytic Reduction (SCR) of NOx with octane as reductant over a Ag/Al2O3 catalyst was carried out using a modified DRIFTS cell coupled to a mass spectrometer Using fast transient cycling switching of H-2 with a time resolution of a few seconds It was possible to differentiate potential reaction intermediates from other moieties that are clearly spectator species Using such a periodic operation mode effects were uncovered that are normally hidden in conventional transient studies which typically consist of a single transient In experiments based on a single transient addition of H-2 to or removal of H-2 from the SCR feed it was found that the changes in the concentrations of gaseous species (products and reactants) were not matched by changes at comparable timescales of the concentration of surface species observed by IR This observation indicates that the majority of sur face species observed by DRIFTS under steady-state reaction conditions are spectators In contrast under fast cycling experimental conditions It was found that a surface isocyanate species had a temporal response that matched that of N-15(2) This suggests that some of the isocyanate species observed by infrared spectroscopy could be important intermediates in the hydrogen-assisted SCR reaction although it is emphasised that this may be dependent on the way in which the infrared spectra are obtained It is concluded that the use of fast transient cycling switching techniques may provide useful mechanistic information under certain circumstances.

TRANSIENT RESONANCE RAMAN AND RAMAN SPECTROELECTROCHEMICAL STUDIES OF CUI COMPLEXES WITH POLYPYRIDYL LIGANDS

Studies by laser flash photolysis, transient Raman spectroscopy, and Raman and UV-vis spectroelectrochemistry are described in which the techniques have been used in parallel to compare the lowest energy charge-transfer excited states of Cu (1) complexes ([Cu(L)2]+ and [ (PPh3)2Cu(L)]+ [L = 2,2'-biquinoline (BIQ) or 6,7-dihydro-5,8-dimethyldibenzo[b,j] [1,10]-phenanthroline (DMCH)) with the species produced by electrochemical reduction in the same group of complexes. Transient resonance Raman spectra for the metal-to-ligand charge-transfer (MLCT) states of [Cu(DMCH)2]+ (1), [Cu(BIQ)2]+ (2), [Cu(DMCH)(PPh3)2]+ (3), and [Cu(BIQ)(PPh3)2]+ (4) are compared with the resonance Raman spectra of the same group of complexes following one-electron electrochemical reduction of the DMCH and BIQ ligands. The UV-vis and resonance Raman evidence suggests that the electrochemical reduction of the [Cu(I)L2]+ species proceeds according to the sequence [LCu(I)L]+ -->e- [LCu0L] -->e- [L.-Cu(I)L.-]-. Several features assignable to modes of the electrochemically generated DMCH.-and BIQ'- radical anions exhibit a close correspondence in both frequency and relative intensity with counterparts in the spectra of the MLCT states of 1 and 2. A notable exception is a band near 1590 cm-1 in the spectra of the electrochemically reduced species which occurs some 15 cm-1 lower in the corresponding spectra of the excited-state species. It is suggested that the shift may reflect the change in oxidation state of the metal center from Cu(I) to Cu(II) which occurs as a result of charge-transfer excitation.

PHOTOPERTURBATION OF THE (1)A-][-(5)T SPIN EQUILIBRIUM IN AN IRON(II) COMPLEX IN SOLUTION VIA LIGAND-FIELD EXCITATION

Variable-temperature magnetic susceptibility measurements in the solid state of the bis complex of tris(1-pyrazolyl)-methane with Fe(II), [Fe(tpm)2](ClO4)2, suggest the existence of singlet-quintet spin crossover with the singlet isomer largely favored at room temperature. In acetonitrile solution, measurement of the absorption spectrum as a function of temperature reveals a spin equilibrium with the quintet population varying from ca. 6% at 233 K to ca. 30% at 295 K. When the complex in solution is irradiated with a laser pulse at wavelengths within the ligand field absorption band of the singlet isomer, ground-state depletion occurs within the pulse duration followed by fast recovery to the original absorbance level with a time constant of 25 +/- 5ns. The recovery time is virtually independent of temperature over the range +23 to -43-degrees-C, but the signal:noise ratio of the transient signals increases with decreasing temperature. The effect was observable at several monitoring wavelengths spanning the LF and MLCT absorption regions of the complex but only when the irradiation wavelength fell within the LF absorption region. Irradiation within the MLCT band produced no effect other than that of laser pulse scatter. The observations are interpreted in terms of photoperturbation of the singlet-quintet spin state equilibrium, which in this case occurs solely through excitation in the ligand field absorption region of the complex and is the first reported instance of this type for a spin-crossover complex in solution.

Electrophysiological, pharmacological and molecular profile of the transient outward rectifying conductance in neonatal rat symapthetic preganglionic neurons in vitro.

Transient outward rectifying conductances or A-like conductances in sympathetic preganglionic neurons (SPN) are prolonged, lasting for hundreds of milliseconds to seconds and are thought to play a key role in the regulation of SPN firing frequency. Here, a multidisciplinary electrophysiological, pharmacological and molecular single-cell rt-PCR approach was used to investigate the kinetics, pharmacological profile and putative K + channel subunits underlying the transient outward rectifying conductance expressed in SPN. SPN expressed a 4-aminopyridine (4-AP) sensitive transient outward rectification with significantly longer decay kinetics than reported for many other central neurons. The conductance and corresponding current in voltage-clamp conditions was also sensitive to the Kv4.2 and Kv4.3 blocker phrixotoxin-2 (1-10 µM) and the blocker of rapidly inactivating Kv channels, pandinotoxin-Ka (50 nM). The conductance and corresponding current was only weakly sensitive to the Kv1 channel blocker tityustoxin-Ka and insensitive to dendrotoxin I (200 nM) and the Kv3.4 channel blocker BDS-II (1 µM). Single-cell RT-PCR revealed mRNA expression for the a-subunits Kv4.1 and Kv4.3 in the majority and Kv1.5 in less than half of SPN. mRNA for accessory ß-subunits was detected for Kvß2 in all SPN with differential expression of mRNA for KChIP1, Kvß1 and Kvß3 and the peptidase homologue DPP6. These data together suggest that the transient outwardly rectifying conductance in SPN is mediated by members of the Kv4 subfamily (Kv4.1 and Kv4.3) in association with the ß-subunit Kvß2. Differential expression of the accessory ß subunits, which may act to modulate channel density and kinetics in SPN, may underlie the prolonged and variable time-course of this conductance in these neurons. © 2011 IBRO.

Influence of water on the carbon dioxide absorption by 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide

The effect of the addition of water on the absorption of carbon dioxide by the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide was studied experimentally by measuring the low-pressure carbon dioxide solubility and the viscosity of the liquid solvent at temperatures from 303 to 323 K. Water is only partially miscible with the ionic liquid up to a mole fraction of 0.302 at 293 K, 0.321 at 303 K and 0.381 at 323 K. It was observed that the solubility of carbon dioxide decreases with the quantity of water from a mole fraction of 2.63 × 10-2 for the pure ionic liquid at 303.4 K to a value of 1.88 × 10-2, a reduction of 30% of the solubility, for a mole fraction of water of 0.28. The viscosity of the liquid solvent also decreases, up to 40% at 303 K, from 28.6 mPa s for the pure ionic liquid to 16.4 mPa s for a water mole fraction of 0.302.

Absorption and antioxidant effects of quercetin from onions, in man

Objective: To investigate the in vivo effects of quercetin following the ingestion of fried onions.

Regulation of transient receptor potential melastatin 8 (TRPM8) channel activity by its short isoforms.

One important mechanism of membrane ion channels regulation involves their non-functional isoforms generated by alternative splicing. However, knowledge of such isoforms for the members of transient receptor potential (TRP) superfamily of ion channels remains quite limited. This study focuses on TRPM member, TRPM8, which functions as a cold receptor in sensory neurons, but is also expressed in tissues not exposed to ambient temperatures, as well as in cancer tissues. We report the cloning from prostate cancer cells of new short-splice variants of TRPM8, termed short TRPM8a (sM8a) and short TRPM8ß (sM8ß). Our results show that both variants are in a closed configuration with the C-terminal tail of the full-size TRPM8 chan-nel, resulting in stabilization of its closed state and thus reducing both its cold sensitivity and its activity. Our findings, therefore, uncover a new mode of the regulation of TRPM8 channel by its splice variants.