Role of cationic gemini surfactants toward enhanced ninhydrin–tryptophan reaction

In this paper we report the effect of dicationic ‘gemini’ surfactants (CH₃)₂C₁₆H₃₃N⁺? (CH₂)_m? N⁺C₁₆H₃₃(CH₃)₂, 2Br^? (where m = 4, 5, 6) on the reaction of ninhydrin with DL ‐tryptophan. The gemini surfactant micellar media are comparatively more effective than their conventional monomeric counterpart cetyltrimethylammonium bromide (CTAB) micelles. Also, whereas typical rate constant (k_ψ) increase and leveling‐off regions, just like CTAB, are observed with geminis, the latter produce a third region of increasing k_ψ at higher concentrations. These subsequent increases are ascribed to changes in micellar morphologies, consistent with changes in ¹H NMR line widths. Quantitative kinetic analysis of the rate constant–[surfactant] data has been performed on the basis of modified pseudophase model. Copyright © 2007 John Wiley & Sons, Ltd.     

Rotational CARS N2 thermometry: validation experiments for the influence of nitrogen spectral line broadening by hydrogen

Rotational coherent anti‐Stokes Raman spectroscopy (CARS) in fuel‐rich hydrocarbon flames, with a large content of hydrogen in the product gases (∼20%), has in previous work shown that evaluated temperatures are raised several tens of Kelvin by taking newly derived N₂ H₂ Raman line widths into account. To validate these results, in this work calibrated temperature measurements at around 300, 500 and 700 K were performed in a cell with binary gas mixtures of nitrogen and hydrogen. The temperature evaluation was made with respect to Raman line widths either from self‐broadened nitrogen only, N₂ N₂ [energy‐corrected‐sudden (ECS)], or by also taking nitrogen broadened by hydrogen, N₂ H₂ [Robert–Bonamy (RB)], Raman line widths into account. With increased amount of hydrogen in the cell at constant temperature, the evaluated CARS temperatures were clearly lowered with the use of Raman line widths from self‐broadened nitrogen only, and the case with inclusion of N₂ H₂ Raman line widths was more successful. The difference in evaluated temperatures between the two different sets increases approximately linearly, reaching 20 K (at T ∼ 300 K), 43 K (at T = 500 K) and 61 K (at T = 700 K) at the highest hydrogen concentration (90%). The results from this work further emphasize the importance of using adequate Raman line widths for accurate rotational CARS thermometry. Copyright © 2010 John Wiley & Sons, Ltd.     

Spectroelectrochemical cell for in situ studies of solid oxide fuel cells

Solid oxide fuel cells (SOFCs) are able to produce electricity and heat from hydrogen‐ or carbon‐containing fuels with high efficiencies and are considered important cornerstones for future sustainable energy systems. Performance, activation and degradation processes are crucial parameters to control before the technology can achieve breakthrough. They have been widely studied, predominately by electrochemical testing with subsequent micro‐structural analysis. In order to be able to develop better SOFCs, it is important to understand how the measured electrochemical performance depends on materials and structural properties, preferably at the atomic level. A characterization of these properties under operation is desired. As SOFCs operate at temperatures around 1073 K, this is a challenge. A spectroelectrochemical cell was designed that is able to study SOFCs at operating temperatures and in the presence of relevant gases. Simultaneous spectroscopic and electrochemical evaluation by using X‐ray absorption spectroscopy and electrochemical impedance spectroscopy is possible.     

A thioester substrate binds to the enzyme Arthrobacter thioesterase in two ionization states: evidence from Raman difference spectroscopy

4‐Hydroxybenzoyl‐CoA (4‐HB‐CoA) thioesterase from Arthrobacter is the final enzyme catalyzing the hydrolysis of 4‐HB‐CoA to produce coenzyme A and 4‐hydroxybenzoic acid in the bacterial 4‐chlorobenzoate dehalogenation pathway. Using a mutation E73A that blocks catalysis, stable complexes of the enzyme and its substrate can be analyzed by Raman difference spectroscopy. Here we have used Raman difference spectroscopy, in the non‐resonance regime, to characterize 4‐HB‐CoA bound in the active site of the E73A thioesterase. In addition, we have characterized complexes of the wild‐type enzyme complexed with the unreactive substrate analog 4‐hydroxyphenacyl‐CoA (4‐HP‐CoA). Both sets of complexes show evidence for two forms of the ligand in the active site: one population has the 4‐hydroxy group protonated, 4‐OH; while the second has the group as the hydroxide, 4‐O⁻. For bound 4‐HP‐CoA, X‐ray data show that glutamate 78 is close to the 4‐OH in the complex and it is likely that this is the proton acceptor for the 4‐OH proton. Although the pK_a of the 4‐OH group on the free substrate in aqueous solution is 8.6, the relative populations of ionized and neutral 4‐HB‐CoA bound to E73A remain invariant between pH 7.3 and 9.8. The invariance with pH suggests that the 4‐OH and the ‐COO⁻ of E78 constitute a tightly coupled pair where their separate pK_a ‘s lose their individual qualities. Narrow band profiles are seen in the CO double bond and C‐S regions, suggesting that the hydrolyzable thioester group is rigidly bound in the active site in a syn gauche conformation. Copyright © 2011 John Wiley & Sons, Ltd.     

Low‐temperature Extensions of the Virial Equation of State for Solar Modeling

Low‐order density expansions cannot adequately describe recombination reactions. Therefore, the usefulness of an exact quantum virial expansion truncated at the order of ?^5/2 is limited to the deeper interior of the Sun, where the plasma is nearly fully ionized. Here, intermediate steps towards full‐fledged solar modeling are presented. They are (i) a smooth numerical representation of the quantum virial expansion and (ii) the construction of a smooth transition to the low‐temperature regime (below 50,000 K), where the virial expansions breaks down due to H recombination. These technical steps are realized for a simplified H‐only plasma; the extension to He and heavier elements will be dealt with later. Ultimately, the outcome will be that solar observations can be used to test the accuracy of the virial equation of state and to compare it with current more phenomenological formalisms (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Local time and Tanaka formula for a multitype Dawson–Watanabe superprocess

In [3] Dynkin defined the local time of a continuous superprocess as a stochastic integral and gave a criterion for existence of local time. Here we prove that the conditions in Dynkin's existence criterion are satisfied by the multitype Dawson–Watanabe superprocess, and give a Tanaka formula‐like representation of the local time which is used to show that the occupation measure of the multitype superprocess is absolutely continuous with respect to an appropriate reference measure, and that the corresponding density coincides a.s. with the local time. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

How the SiC substrate impacts graphene's atomic and electronic structure

Graphene, the two‐dimensional form of carbon presents outstanding electronic and transport properties. This gives hope for the development of applications in nanoelectronics. However, for industrial purpose, graphene has to be supported by a substrate. We focus here on the graphene‐on‐SiC system to discuss how the SiC substrate interacts with the graphene layer and to show the effect of the interface on graphene atomic and electronic structures.

     

Effect of Solute‐Polymer Interactions on Sorption and Diffusion in Polyacrylamide Gels

Solute‐polymer interactions can exert a large effect on selective sorption and permeation in polyacrylamide (PAAm) gels. In order to investigate this effect, three probe polyelectrolytes, sodium polystyrene sulphonate (PSS), polyvinylpyrrolidone (PVP), and sulfonated polyaniline (SPANI), were chosen as probe species in sorption, release, and permeation experiments in PAAm gels. For PAAm gels with trapped SPANI, FTIR spectroscopy has confirmed that there exists hydrogen‐bonding between SPANI and PAAm. In addition, rigid‐chain SPANI has an intense tendency to aggregate; it is likely that the effective chains of the PAAm matrices are enwrapped in these aggregates. Hydrogen‐bonding and aggregation resulted in that the release kinetics of SPANI from PAAm gels exhibited a remarkable “lag time”, as long as 100 h (lag period means that in the initial period there is no detectable SPANI released from PAAm gels.), the releasing rate of SPANI was very slow, and the selective sorption of SPANI in PAAm gels was extremely high. On the other hand, the release and permeation of PVP and PSS through PAAm gels were much faster than SPANI, and the selective sorption were close to unity. From these facts it could be deduced that there is no or only weak interaction between PAAm and PSS (or PVP). Adding of concentrated support electrolyte resulted in decrease of the release rate and a two‐magnitude decrease of the calculated diffusion coefficients of PSS; the effect of support electrolyte on release and permeation of PSS was partly attributed to the electrostatic interaction.