Molecular films of water-miscible ionic liquids formed on glassy carbon electrodes: characterization and electrochemical applications

This letter describes the formation and possible electrochemical applications of molecular films of water-miscible imidazolium-based ionic liquids (ILs) on glassy carbon (GC) electrodes. X-ray photoelectron spectroscopy (XPS) and electrochemical results indicate that the water-miscible ILs used in this study can interact with the GC electrode and form molecular films on the electrode surface. The formed molecular films are found to possess striking electrochemical properties such as electrocatalysis toward ascorbic acid (AA) and the capability to facilitate direct electron transfer of horseradish peroxidase (HRP). This demonstration would pave the way for new electrochemical applications of water-miscible ILs and is envisaged to be useful for the investigation of the electrochemical properties of water-miscible ILs in aqueous media provided the same counteranion is used as the supporting electrolyte.     

An investigation of mononuclear and binuclear palladium(II) complexes of egta (egta = glycine,N,N′-(1,2-ethanediylbis(oxy-2,1-ethanediyl)bis[N-carboxymethyl]) by 1H-, 13C- and 15N-n.m.r. methods

1:1 and 2:1 palladium(II) complexes of egta^4– (egta^4– = glycine, N,N-(1,2-ethanediylbis)(oxy-2,1-ethanediyl)bis[N-carboxymethyl]) were prepared by 1:1 and 2:1 addition of K₂PdCl₄ to K₄egta, and examined by ¹H-, ¹³C- and ¹⁵N-n.m.r. methods. The 1:1 complex, [Pd(egta)]^2– in solution, utilizes a square-planar coordination comprised of two nitrogen and two glycinato carboxylate donors of egta^4–, leaving two glycinato carboxylates pendant. The complex has a cis-(R,S) stereochemistry which places both pendant carboxylates below the PdN₂O₂ square plane and the tether backbone of egta^4– in the up, up sense above the same plane. The cis-(R,S) assignment was assisted by computer simulations of the ¹³C-n.m.r. spectrum for four possible isomers. Only cis-(R,S) and trans-(R,R) calculated ¹³C-spectra were compatible with the observed ¹³C-n.m.r. pattern. The HH NOESY spectrum of [Pd(egta)]^2– detects long range coupling of the backbone –OCH₂CH₂O– linkage with both coordinated and pendant glycinato CH₂ moieties. The cis-(R,S) isomer's tortional movements allow such contacts whereas a trans-(R,R) isomer does not. The 2:1 complex, [Pd₂(egta)(H₂O)₂] in solution has an extended-chain structure with each palladium(II) center coordinated in the mer-iminodiacetate-like coordination with two bound glycinato-functionalities.     

An in situ STM study on the long-range surface restructuring of Au(1 1 1) in a non-chloroaluminumated ionic liquid

We report an in situ STM study of a potential-dependent long-range surface restructuring of Au(1 1 1) electrode in neat 1-butyl-3-methylimidazolium tetrafluoroborates (BMIBF₄) ionic liquid. Au(1 1 1) undergoes a significant long-range surface restructuring upon cathodic excursion to −1.0 V vs. Pt quasi-reference. The restructuring involves the formation of tiny pits, which then develops into a stable worm-like network with an average width of the network grids 2 nm. Electrochemical annealing occurs at the cathodic limit with the presence of a reduction product of cation BMI⁺. A smooth surface is recovered with the appearance of the typical (√3 × 22) reconstruction of Au(1 1 1). The surface restructuring is reestablished upon anodic excursion to −1.3 V after the adsorbed reduction product is oxidized. The long-range surface restructuring phenomenon is tentatively explained as a result of partial charge transfer to the weakly adsorbed BMI⁺, which reduces the metal–metal cohesive energy. In addition, the synergetic effect of the counter anion BF₄⁻ may also be involved. The results provide a knowledge of Au(1 1 1) electrode behavior in the neat ionic liquid and are beneficial to understanding in situ STM results involving surface morphological changes in such a media.     

Liquid chromatography particle beam-mass spectrometry with massive cluster impact

A new liquid chromatography-mass spectrometry technique is described that utilizes a particle beam interface to transport and deposit desolvated analyte molecules onto a target surface that is bombarded by a primary beam of massive multiply charged glycerol cluster ions to generate secondary ions for mass analysis. The massive cluster ion beam is generated by electrohydrodynamic emission from a solution of 1. 5-M ammonium acetate in glycerol. In the present instrumental configuration the massive cluster ion gun is placed above the target probe and the particle beam interface is connected through a side port of the mass spectrometer. The massive cluster ion beam and particle beam are intercepted by a target surface substituted for a conventional ion volume. The target surface is positioned such that it is ～ 45 ° to the primary cluster ion beam, the particle beam, and the mass analyzer axis. This geometric orientation represents a compromise among the performances of these three elements. The feasibility of this liquid chromatography-particle beam on-line with massive cluster impact is demonstrated by flow injections of acetylcholine chloride and gramicidin S. Spectra generated from this preliminary study indicate promise for routine liquid chromatography-mass spectrometry of polar compounds by using a robust inlet and an effective generation of secondary ions without an added matrix.     

Fast electron transfer repair of oxidizing OH adduct of dGMP by chlorogenic acid

ＥｘｔｅｎｓｉｖｅｓｔｕｄｉｅｓｏｆｒａｄｉａｔｉｏｎｏｒｃｈｅｍｉｃａｌｉｎｊｕｒｙｏｆｂｉｏｌｏｇｉｃａｌｔａｒｇｅｔｍｏｌｅｃｕｌｅｓｄｅｍｏｎｓｔｒａｔｅｔｈａｔＯＨｒａｄｉｃａｌ,ｔｈｅｍｏｓｔｒｅａｃｔｉｖｅｏｘｙｇｅｎｓｐｅｃｉｅｓ,ｒｅａｃｔｓｗｉｔｈｂｉｏｌｏｇｉｃａｌｍａｃｒｏｍｏｌｅｃｕｌｅｓ,ｓｕｃｈａｓＤＮＡ,ｉｎｄｕｃｉｎｇｂａｓｅａｌｔｅｒａｔｉｏｎｓ,ｂａｓｉｃｓｉｔｅｓ,ａｎｄｓｔｒａｎｄｂｒｅａｋｓ,ｒｅｓｕｌｔｅｄｉｎｖａｒｉｏｕｓｐａｔｈｏｇｅｎｅｓｉｓ,ｓｕｃｈ…     

Synthesis of Insect Sex Pheromones and Their Homologues I. (Z,E)-9, 11-Alkadienyl Acetates

(Z, E)-9, 11-Tetradecadienyl-l-acetate (1), a major component of the sex pheromone of Spodoptera litura (F.), and (Z, E}-9, 11-pentadecadienyl-1-acetate (2) were synthesized by the Wittig reaction between (E)-2-alkenal (3) and the ylid derived from 9-hydroxynonyltriphenylphosphonium bromide (4).     

Photolysis of Isoniazid

The UV light irradiation of isoniazid (I) in methanol four products, isonicotinic acid (II), isonicotinamide (III), N, N′-bis(isonicotinic acid)hydrazide (IV) and isonicotinaldehyde isonicotinyl hydrazone (V), in ethanol three products, (III), (IV) and acetaldehyde isonicotinyl hydrazone (VI) were isolated and identified. Also, the photoreaction mechanism of isoniazid in methanol and ethanol were discussed.     

Chiral palladium template promoted asymmetric hydrophosphination reaction between diphenylphosphine and vinylphosphines

An organopalladium complex containing ortho-metalated (S)-(1-(dimethylamino)ethyl)naphthalene as the chiral auxiliary has been used to promote the asymmetric hydrophosphination reactions between diphenylphosphine and (E)- or (Z)-diphenyl-1-propenylphosphine in high regio- and stereoselectivities under mild conditions. Hydrophosphination of (Z)-diphenyl-1-propenylphosphine with diphenylphosphine gave (S)-(-)-prophos as the major product. Using the same chiral metal template, the corresponding hydrophosphination reaction with (E)-diphenyl-1-propenylphosphine gave (R)-(+)-prophos predominantly. The hydrophosphination reactions generated the asymmetric diphosphines as bidentate chelates on the chiral naphthylamine palladium templates. The template products obtained undergo cis-trans isomerization in solution to form an equilibrium mixture of regioisomers. X-ray analysis of the major template products obtained from the hydrophosphination of (Z)-diphenyl-1-propenylphosphine reveals that the two regioisomers are cocrystallized in a 1:1 ratio. The naphthylamine auxiliary could be removed chemoselectively from the template products by treatment with concentrated hydrochloric acid to form the corresponding optically pure neutral complexes [(R)- or (S)-(prophos)PdCl(2)]. Subsequently, the (R)- and (S)-dichloro complexes undergo ligand displacement with aqueous cyanide to generate the corresponding optically pure diphosphine ligands in high yields. Mechanistic pathways explaining the stereoselectivity of the chiral organopalladium template promoted hydrophosphination reactions are also proposed.     

Mössbauer Spectroscopic Studies of Supported α-Fe2O3 and Fe Catalysts II: The Effect of the Second Metal Addition

The effect of the addition of a second metals such as Zn and Ni on the calcinaton and reduction of alumina, magnesia and silicasupported iron catalysis with total iron loading of 5wt% is investigated by Mössbauer spectroscopy. It is shown that the reducibility of supported α-Fe₂O₃ is gradually increased by adding the second metal. The values of the magnetic hyperfine field obtained from Mössbauer spectra for the Zn or Ni-added α-Fe₂O₃ or Fe catalysts decreased with increasing second metal loading.     

Chiral metallacyclophanes: self-assembly, characterization, and application in asymmetric catalysis

[structure: see text] A family of chiral metallacyclophanes has been readily assembled based on robust Pt-acetylide linkage and characterized by a variety of spectroscopic techniques and X-ray crystallography. The steric congestion around the chiral dihydroxy groups in rigid metallacyclophane 4 prevents their reactions with Ti(O(i)()Pr)(4) to form active catalysts for enantioselective diethylzinc additions to aromatic aldehydes. In contrast, chiral dihydroxy groups in more flexible unclosed metallacyclophane 5 are effective ligands for enantioselective catalytic diethylzinc additions to aromatic aldehydes.