Electrochemical reduction of NO on La2-x Sr x NiO4 based electrodes

The series La_2 − x Sr _x NiO₄ (x = 0.0, 0.05, 0.15, 0.25, 0.35, and 1.0) was tested for functionality as electrode materials for direct electrochemical reduction of NO. The materials were tested using cyclic voltammetry in 1% NO and 10% O₂ in Ar on a cone-shaped electrode. The best materials for the electrochemical reduction of NO are La₂NiO₄ and LaSrNiO₄, which have current densities for NO reduction 1.82 and 7.09 times higher, respectively, than for O₂ at 400 °C. Increasing the temperature decreased the ability to reduce NO before O₂ while the activity increased. The adsorbed species during direct decomposition was attempted, clarified using X-ray absorption near-edge structure experiments and thermogravimetry, but no conclusive results were obtained.     

Spectroscopy and electrochemistry of cytochrome P450 BM3-surfactant film assemblies

We report analyses of electrochemical and spectroscopic measurements on cytochrome P450 BM3 (BM3) in didodecyldimethylammonium bromide (DDAB) surfactant films. Electronic absorption spectra of BM3-DDAB films on silica slides reveal the characteristic low-spin FeIII heme absorption maximum at 418 nm. A prominent peak in the absorption spectrum of BM3 FeII-CO in a DDAB dispersion is at 448 nm; in spectra of aged samples, a shoulder at approximately 420 nm is present. Infrared absorption spectra of the BM3 FeII-CO complex in DDAB dispersions feature a time-dependent shift of the carbonyl stretching frequency from 1950 to 2080 cm(-1). Voltammetry of BM3-DDAB films on graphite electrodes gave the following results: FeIII/II E(1/2) at -260 mV (vs SCE), approximately 300 mV positive of the value measured in solution; DeltaS degrees (rc), DeltaS degrees , and DeltaH degrees values for water-ligated BM3 in DDAB are -98 J mol(-1) K(-1), -163 J mol(-1) K(-1), and -47 kJ mol(-1), respectively; values for the imidazole-ligated enzyme are -8 J mol(-1) K(-1), -73 J mol(-1) K(-1), and -21 kJ mol(-1). Taken together, the data suggest that BM3 adopts a compact conformation within DDAB that in turn strengthens hydrogen bonding interactions with the heme axial cysteine, producing a P420-like species with decreased electron density around the metal center.     

Effects of the type of crosslink on viscoelastic properties of natural rubber

The viscoelastic properties of various crosslinked natural rubbers, NR, were investigated by mechanical spectroscopy. The glass transition temperature, T_g, was found to be dependent on both the crosslink density and the crosslink type. Higher values of T_g were obtained for sulfur-crosslinked NR than for peroxide-crosslinked NR at the same crosslink density. The greater influence of the sulfur content on T_g may be attributed to polysulfidic crosslinks and cyclic sulfide structures favored at high sulfur contents. Sulfur-vulcanized NRs with monosulfidic crosslinks, favored at relatively high accelerator/sulfur ratios, have properties more similar to the peroxide-cured NR with simple carbon(SINGLE BOND)carbon crosslinks covalent bonds, resulting in only small shifts in T_g. A qualitative analysis of monosulfidic crosslinks and polysulfidic structures was performed with ¹³C solid-state NMR spectroscopy. The storage modulus, E′, in the rubbery plateau region increased with increasing crosslink density. However, the crosslink type did not influence the moduli values as much as it influenced the T_g values. Different methods of detecting the crosslink density were also discussed. © 1996 John Wiley & Sons, Inc.     

A rapid and specific derivatization procedure to identify acyl‐glucuronides by mass spectrometry

A simple procedure is described to identify acyl‐glucuronides by coupled liquid chromatography/mass spectrometry after derivatization to a hydroxamic acid with hydroxylamine. The reaction specificity obviates the need for isolation of the acyl‐glucuronide from an extract. Glucuronides derived from carbamic acids, and alkyl‐ and aromatic amines, are inert to the derivatization reaction conditions, making the hydroxamic acid derivative a fingerprint for acyl‐glucuronides. Copyright © 2010 John Wiley & Sons, Ltd.     

Tetrachlorinated Tetraazaperopyrenes (TAPPs): Highly Fluorescent Dyes and Semiconductors for Air‐Stable Organic n‐Channel Transistors and Complementary Circuits

A range of 2,9‐perfluoroalkyl‐substituted tetraazaperopyrene (TAPP) derivatives ( 1 – 5 ) was synthesised by reacting 4,9‐diamino‐3,10‐perylenequinone diimine (DPDI) with the corresponding carboxylic acid chloride or anhydride in the presence of a base. The reaction of compounds 1 – 4 with dichloroisocyanuric acid (DIC) in concentrated sulphuric acid resulted in the fourfold substitution of the tetraazaperopyrene core, yielding the 2,9‐bisperfluoroalkyl‐4,7,11,14‐tetrachloro‐1,3,8,10‐tetraazaperopyrenes 6 – 9 , respectively. The optical and electrochemical data demonstrate the drastic influence of the core substitution on the properties. All compounds are highly luminescent (fluorescence quantum yields of up to Φ=0.8). The LUMO energies of the tetrachlorinated TAPP derivatives (determined by cyclic voltammetry and computed by DFT calulations) were found to be below ?4 eV. In the course of this work the performance of TAPP derivatives in organic thin‐film transistors (TFTs) was investigated, and their n‐channel characteristics with field‐effect mobilities of up to 0.14 cm² V^?1 s^?1 and an on/off current ratio of >10⁶ were confirmed. Long‐term stabilities of 3–4 months under ambient conditions of the devices were established. Complementary inverters and ring oscillators with n‐channel TFTs based on compound 8 and p‐channel TFTs based on dinaphtho‐[2,3‐b:2′,3′‐f]thieno[3,2‐b]thiophene (DNTT) were fabricated on a glass substrate.     

Square-planar coordinated polyanions of palladium, platinum, and gold stannaborate [SnB11H11]2- coordination chemistry

The tetrasubstituted polyanions of platinum, palladium, and gold [M(SnB(11)H(11))(4)](x-) (x=6, M=Pd, Pt; x=5, M=Au) have been prepared and characterized by single-crystal X-ray diffraction, elemental analysis, IR, Raman, (11)B, and (119)Sn heteronuclear NMR spectroscopy. In the case of the platinum derivative [Bu(3)MeN](6)[Pt(SnB(11)H(11))(4)] (2) (119)Sn M?ssbauer spectroscopy has been carried out. The isolated salts are stable towards moisture and air and the complexes 2 and 3 were treated with 1,3-bis(diphenylphosphino)propane (dppp) to give the respective substitution products [Bu(3)MeN](2)[(dppp)M(SnB(11)H(11))(2)] (M=Pd, Pt).     

Synthesis of sugar oxime ether surfactants

A straightforward synthesis of a novel class of sugar surfactants is described. The key step is the chemoselective condensation of a hydrophobic alkoxyamine with the resident aldehyde/ketone moiety on a hydrophilic sugar. Neither protection/deprotection of the sugars nor extensive product purification is required. The method allows for the facile adjustment of hydrophobic and hydrophilic domains of the sugar oxime ether surfactant and uses inexpensive, readily accessible, and renewable materials.     

Two Hexagonal Series of Lanthanoid(III) Oxide Fluoride Selenides: M6O2F8Se3 (M = La – Nd) and M2OF2Se (M = Nd,Sm, Gd – Ho)

Two hexagonal series of lanthanoid(III) oxide fluoride selenides with similar structure types can be obtained by the reaction of the components MF₃, M₂O₃, M, and Se in sealed niobium tubes at 850 °C using CsI as fluxing agent. The compounds with the lighter and larger representatives (M = La – Nd) occur with the formula M₆O₂F₈Se₃, whereas with the heavier and smaller ones (M = Nd, Sm, Gd – Ho) their composition is M₂OF₂Se. For both systems single‐crystal determinations were used in all cases. The compounds crystallize in the hexagonal crystal system (space group: P6₃/m) with lattice parameters of a = 1394–1331 pm and c = 403–372 pm (Z = 2 for M₆O₂F₈Se₃ and Z = 6 for M₂OF₂Se). The (M1)³⁺ cations show different square antiprismatic coordination spheres with or without an extra capping fluoride anion. All (M2)³⁺ cations exhibit a ninefold coordination environment shaped as tricapped trigonal prism. In both structure types the Se^2– anions are sixfold coordinated as trigonal prisms of M³⁺ cations, being first condensed by edges to generate trimeric units and then via faces to form strands running along [001]. The light anions reside either in threefold triangular or in fourfold tetrahedral cationic coordination. For charge compensation, both structures have to contain a certain amount of oxide besides fluoride anions. Since F^– and O^2– can not be distinguished by X‐ray diffraction, bond‐valence calculations were used to address the problem of their adjunction to the available crystallographic sites.