The magnetic concentration gradient force—Is it real?

There are suggestions in the electrochemical literature that a body force F _∇c acts when an electrolyte with a non-uniform concentration c of paramagnetic ions is subject to a uniform magnetic field. We demonstrate, experimentally and theoretically, that no such magnetic body force exists, to first order. A second-order correction associated with the demagnetizing field does lead to a very small concentration-dependent body force, which is not expected to produce any observable effect in electrochemistry. Contribution to special issue on Magnetic field effects in Electrochemistry.

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Spectroscopic evaluation of a compact magnetically boosted radiofrequency glow discharge for time-of-flight mass spectrometry

A compact magnetically boosted radiofrequency glow discharge (GD) has been designed, constructed and its analytical potential evaluated by its coupling to a mass spectrometer (MS). Simple modifications to the original source configuration permitted the insertion of permanent magnets. Small cylindrical Nd–Fe–B magnets (∅ = 4 mm, h = 10 mm) were placed in an in-house-modified GD holder disc that allows easy and fast exchange of the magnets. The different processes taking place within the GD plasma under the influence of a magnetic field, such as sputtering, ionisation processes and ion transport into the MS, were studied using different GD operating conditions. Changes to the ionisation and ion transport efficiency caused by the magnetic field were studied using an rf-GD-TOFMS setup. A magnetic field of 60–75 gauss (G) was found not to affect the sputtering rates but to enhance the analyte ion signal intensities while decreasing the Ar species ion signals. Moreover, magnetic fields in this range were shown not to modify the crater shapes, enabling the fast and sensitive high depth resolved analysis of relatively thick coated samples (micrometre) by using the designed compact magnetically boosted rf-GD-TOFMS.

A model for high-surface-area porous Nafion™-bonded cathodes operating in hydrogen–oxygen proton exchange membrane fuel cells (PEMFCs)

A critical discussion of dioxygen reduction kinetics using the Tafel (for the irreversible cathode process) and the Butler–Volmer (anode process) rate equations has been used to evaluate the accuracy of “standard” modeling interpretations of experimental cell potential current (E–I) plots. The potential–current curve for what is believed to be an optimized Nafion™-bonded fuel cell cathode was analyzed. It appears to behave as a well-ordered diffusional system and shows high electrocatalyst utilization based on its electrocatalytic and gas diffusion characteristics. The electrode appears to perform as expected, without any anomalous characteristics showing any lower than expected electrocatalyst utilization. Any improvement in electrode performance, which is certainly desirable, seems to demand an improved diffusional structure, barring any potential (although unlikely) change in electrochemical kinetic characteristics.

On the open-circuit interaction between methanol and oxidized platinum electrodes

In the present work, results of the interaction between methanol and oxidized platinum surfaces as studied via transients of open-circuit potentials are presented. The surface oxidation before the exposure to interaction with 0.5 M methanol was performed at different polarization times at 1.4 V vs reversible hydrogen electrode (RHE). In spite of the small changes in the initial oxide content, the increase of the pre-polarization time induces a considerable increase of the time needed for the oxide consumption during its interaction with methanol. The influence of the identity of the chemisorbing anion on the transients was also investigated in the following media: 0.1 M HClO₄, 0.5 M H₂SO₄, and 0.5 M H₂SO₄ + 0.1 mM Cl⁻. It was observed that the transient time increases with the energy of anion chemisorption and, more importantly, without a change in the shape of the transient, meaning that free platinum sites are available at the topmost layer all over the transient and not only in the potential region of small oxide ‘coverage’. The impact of the pre-polarization time and the effect of anion chemisorption on the transients are rationalized in terms of the presence of surface and subsurface oxygen driven by place exchange.

Fast-scan cyclic voltammetry for the detection of tyramine and octopamine

Tyramine and octopamine are biogenic amine neurotransmitters in invertebrates that have functions analogous to those of the adrenergic system in vertebrates. Trace amounts of these neurotransmitters have also been identified in mammals. The purpose of this study was to develop an electrochemical method using fast-scan cyclic voltammetry at carbon-fiber microelectrodes to detect fast changes in tyramine and octopamine. Because tyramine is known to polymerize and passivate electrode surfaces, waveform parameters were optimized to prevent passivation. No fouling was observed for octopamine when the electrode was scanned from 0.1 to 1.3 V and back at 600 V/s, while a small decrease of less than 10% of the signal was seen for 15 repeated exposures to tyramine. The technique has limits of detection of 18 nM for tyramine and 30 nM for octopamine, much lower than expected levels in insects and lower than basal levels in some brain regions of mammals. Current was linear with concentration up to 5 μM. This voltammetry technique should be useful for measuring tyramine and octopamine changes in insects, such as the fruit fly, Drosophila melanogaster.

Molecular and crystal structure of ethylene acetal of <Emphasis Type="Italic">endo</Emphasis>-<Emphasis Type="Italic">endo</Emphasis>-3-trityloxymethylbicyclo[3.3.1]nonane-2-on-7-ol

Molecular structure of ethylene acetal of 3-trityloxymethylbicyclo[3.3.1]nonane-2-on-7-ol (3) was determined by X-ray investigation. It was revealed that 3 has endo-endo-configuration and adopt chair-boat-conformation. The distortion of rings was evaluated by calculation of the Zefirov–Palyulin and Cremer–Pople puckering parameters. Failure of esterification of 3 was rationalized in terms of steric hindrance and intramolecular hydrogen bonding.

Mesogenic and magnetic behavior in cobalt(II) and iron(II) compounds with long alkyl chains

Abstract  Metal complexes with long alkyl chains [Co(C16-terpy)₃](BF₄)₂ (1), [Fe(C16-terpy)₂](BF₄)₂ (2), [Co(C16-terpy)₂](BPh₄)₂ (3), [Co(C14-terpy)₂](BF₄)₂ (4), and [Fe(C12C10C5-terpy)₂](BF₄)₂ (5) were synthesized and their physical properties characterized, where C16-terpy, C14-terpy, and C12C10C5-terpy are 4′-hexadecyloxy-2,2′:6′,2′′-terpyridine, 4′-tetradecyloxy-2,2′:6′,2′′-terpyridine, and 4′-5′′′-decyl-1′′′-heptadecyloxy-2,2′:6′,2″-terpyridine, respectively. Complexes 1, 2, and 5 exhibited liquid–crystal properties in the temperature ranges of 371–528 K and 466–556 K, and 88–523 K, respectively. Variable-temperature magnetic susceptibility measurements revealed that the Co(II) complexes 1 and 4 exhibited unique spin transitions (T _1/2↓ = 217 K and T _1/2↑ = 260 K for 1 and T _1/2↓ = 250 K and T _1/2↑ = 307 K for 4), so-called ‘reverse spin transition,’ induced by structural phase transitions. Complex 3 exhibited gradual spin-crossover behavior (T _1/2 = 160 K.), and complex 5 exhibited spin transitions (T _1/2↑ = 288 K and T _1/2↓ = 284 K) at the liquid crystal transition temperature. Compounds with multifunction, i.e., magnetic and liquid–crystal properties, are important in the development of molecular materials. Graphical Abstract  

NEMCA effect: why are the work function changes of the gas exposed catalyst-electrode surface one-to-one related to the changes in the catalyst working electrode potential?

In the present work, an important point concerning the NEMCA effect is addressed. We analyse the reasons why the changes in the work function of the gas exposed catalyst-electrode surface are one to one related to the changes in the catalyst working electrode potential E with respect to a reference electrode. It is concluded that this is due to the unique properties of the catalyst/solid electrolyte interface: the structure of the double layer in this region is very different from that in liquid electrolytes, being the potential difference at this interface mainly determined by the specific adsorption of the mobile species in the solid electrolyte.

A Chain Catalytic Reaction Involving Pd Cluster as Chain Carrier

   α−Alkyl- and α,α′-dialkyl-substituted benzylic alcohols PhCR′R′′OH (R′=H, Me, Et, Bu; R′′=H, Me) are transformed to the corresponding dilbenzylic ethers and water in acid-free neat substrate media shortly after the addition of the palladium(I) cluster [Pd₄(CO)₄(OAc)₄] (1). During the catalytic reaction occurring under anaerobic conditions, cluster 1 is gradually decomposed to form Pd black, whereas neither original cluster 1 nor Pd black is responsible for the observed reaction. The true reaction catalyst is generated from cluster 1 after a short induction period. On the basis of the reaction kinetics and the HREM, X-ray diffraction, DTA-TG, and elemental analysis data, the catalytic dehydration is suggested to occur through a nonradical chain mechanism involving an unstable intermediate Pd cluster as the chain carrier.

Supramolecular architecture of phenylcarbamoylated acetone oxime 1,1-diisopropyl-3-phenylurea] complex

Carbamoylated oximes 1 form 1:1 molecular complexes 4 with N,N-dialkyl-N′-phenylurea when stirred in THF or ether at room temperature for short time in good yields. The molecular complexes 4a–e were isolated and characterized by analytical and spectral means. X-ray crystallographic analysis for complex 4a was performed. In this paper, we report the use of complex 4a and its moieties as building blocks to form non-interacting polymeric zigzag chains by inter- and intramolecular hydrogen bonds along b-axis, and details of supramolecular architecture of 4a. There is a intramolecular H–H interaction between hydrogen of urea NH and neighboring hydrogen of diisopropyl's CH linked to the other urea nitrogen. In addition, to obtain the most favorable orientation of the moieties of the title complex, PM3 semi-empirical quantum mechanical calculations were performed and then results from X-ray crystallography and computational modeling were compared.

Synthesis and Crystal Structure of a Heteronuclear Fe–Ru Silyl Complex*

The reaction of the iron metalate [Fe{Si(OMe)₃}(CO)₃(dppm-P)]⁻ (1b) with [Ru(CO)₃Cl(μ-Cl)]₂ afforded the heterodinuclear complex [(OC)₃{(MeO)₃Si}Fe(μ-dppm)Ru(CO)₃Cl)] (Fe–Ru) (3) in which a long Fe–Ru separation of 2.956(1) ? has been crystallographically evidenced. It was shown by density functional theory (DFT) calculations to correspond to the minimum-energy structure. Upon treatment of the corresponding hydrido complex [HFe{Si(OMe)₃}(CO)₃(dppm-P)] (1a) with [Ru(CO)₃Cl(μ-Cl)]₂, the chloride-bridged tetranuclear hydrido complex [(OC)₃{(MeO)₃Si}Fe(H)(μ-dppm)Ru(CO)₂Cl(μ-Cl)]₂ (4) was formed in which the Fe and Ru centers are only linked via bridging dppm ligands. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

In defence of the correlation coefficient

The relationship between calibrated range, residual standard deviation and correlation coefficient r is discussed. It is shown that in typical chemical calibration applications with appropriately distributed calibration points (particularly, with range comparable to mean and with approximately even or with ‘successive dilution’ spacing), the linear correlation coefficient has valid application as a routine criterion for acceptable fit if used with due care.

Modeling of solvent viscosity effects on the electroreduction of Pt(II) aquachlorocomplexes

Solvent dynamics effects on the electroreduction of [PtCl₃(H₂O)]⁻ at a mercury electrode are explored in the framework of Sumi–Marcus model using an efficient computational scheme. According to results of density functional calculations, the second electron transfer step may be regarded as rate controlling. The nonmonotonous influence of solvent viscosity on the reaction rate is predicted and explained in terms of the saddle point avoidance. The results of model calculations are employed to interpret experimental data reported earlier in the literature.

Complementary precursor ion and neutral loss scan mode tandem mass spectrometry for the analysis of glycerophosphatidylethanolamine lipids from whole rat retina

A “shotgun” tandem mass spectrometry (MS) approach involving the use of multiple lipid-class-specific precursor ion and neutral loss scan mode experiments has been employed to identify and characterize the glycerophosphatidylethanolamine (GPEtn) lipids that were present within a crude lipid extract of a normal rat retina, obtained with minimal sample handling prior to analysis. Characterization of these lipids was performed by complementary analysis of their protonated and deprotonated precursor ions, as well as their various ionic adducts (e.g., Na⁺, Cl^-), using a triple-quadrupole mass spectrometer. Notably, the application of novel precursor ion and neutral loss scans of m/z 164 and m/z 43, respectively, for the specific identification of sodiated GPEtn precursor ions following the addition of 500 μM NaCl to the crude lipid extracts was demonstrated. The use of these novel MS/MS scans in parallel provided simplified MS/MS spectra and enhanced the detection of 1-alkenyl, 2-acyl (plasmenyl) GPEtn lipids relative to the positive ion mode neutral loss m/z 141 commonly used for GPEtn analysis. Furthermore, the novel use of a “low energy” neutral loss scan mode experiment to monitor for the exclusive loss of 36m/z (HCl) from [M+Cl]^- GPEtn adducts was demonstrated to provide a more than 25-fold enhancement for the detection of GPEtn lipids in negative ion mode analysis. Subsequent “high-energy” pseudo MS³ product ion scans on the precursor ions identified from this experiment were then employed to rapidly characterize the fatty acyl chain substituents of the GPEtn lipids. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

Electron free energy levels in oxidic solutions: relating oxidation potentials in aqueous and non-aqueous systems

We provide background to the problem of describing the state of redox couples in different types of solvent media ranging from acidic aqueous solutions to high temperature molten silicates, pointing out the essential similarity between these solvent media in Lewis acid–base terms. We review the adaptation of the Gurney proton energy level diagram approach to the case of electron transfer processes. Using data from various spectroscopic and analytical chemistry sources, we review the construction of electron free energy level diagrams for redox couples in aqueous and non-aqueous systems using, as a common reference, the potential of the oxygen gas (1 atm)/oxide ion couple in the solution of interest. We emphasize the anomalous effect of “oxide ion activity” (mean ionic activity of alkali oxide) on the state of equilibrium and interpret this in terms of oxide ion transfers that accompany electron transfers. After showing the essential agreement between recent direct electrochemical assessments of the energy levels and those deduced in our original analysis of oxidic melts of different glass formers, we provide an interpretation of the apparent “oxide ion transfer” in terms of the differential medium polarization by the two redox species involved in the equilibrium. We anticipate the extension of these ideas to redox chemistry in the currently burgeoning field of “ionic liquids” in its recent ambient temperature liquid incarnation. Dedicated to the 85th birthday of John O’M. Bockris.

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Core-shell structured electrode materials for lithium ion batteries

Recent progress in studies of several types of core-shell structured electrode materials, including TiO₂/C, Si/C, Si/SiO _x , LiCoO₂/C, and LiFePO₄/C nanocomposites, including details of their preparation and their electrochemical performance is briefly reviewed. Results clearly show that the coating shell can effectively prevent the aggregation of the nanosized cores, which are the electrochemically active materials. In addition, the diffusion coefficients of lithium ions can be increased, and the reversibility of lithium intercalation and deintercalation is improved. As a result, the cycling behavior is greatly improved. The reviewed results suggest that core-shell nanocomposites are a good starting point for further development of new promising electrode materials.

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Bonding in β-diketiminate boron and its analogues

Bonding analysis in β-diketiminate boron and related systems has been performed. For the optimized geometries (MP2/aug-cc-pVTZ), the post-SCF electron density function has been produced and its topological parameters have been analyzed according to Atoms in Molecules Quantum Theory approach. The B–N bond has characteristics similar to those found for TM–ligand bonding. The symmetric character of the B–N interaction found for the β-diketiminate boron results from the fully π-electron delocalized character of the β-diketiminate moiety. If the π-electron system in NCCCN sequence of bonds is localized, the asymmetric B–N bonding is enforced. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

Electrochemical and photoelectrochemical characterization of CuFeO2 single crystal

CuFeO₂ single crystal, synthesized by the flux method, is a narrow band gap semiconductor crystallizing in the delafossite structure with a direct optical transition of 1.63 eV. The oxide exhibits a good chemical stability; the semi-logarithmic plot gave an exchange current density of 0.60 μA cm⁻² in KCl (0.5 M) electrolyte. CuFeO₂ shows p-type conductivity; the origin of acceptors Cu²⁺ results from oxygen insertion in the layered lattice where most of excess holes are trapped in surface-polaron states. The electrochemical study is confined in the (a,b) plane and reversible oxygen intercalation is evidenced from the intensity potential characteristics. The detailed photoelectrochemical studies have been reported for the first time on the single crystal. The photocurrent is ascribed to the transfer Cu⁺:3d→3d. The capacitance measurement (C⁻²–V) shows a linear behavior from which a flat band potential of +0.54 V_SCE and a density N _A of 1.60 × 10¹⁸ cm⁻³ were determined. The valence band, located at 5.33 eV below vacuum, is made up of Cu-3d orbital typical of delafossite oxides. The Nyquist plot shows a semicircle attributed to a capacitive behavior with a low density of surface states within the gap. The centre is localized below the real axis with an angle of 16.2° ascribed to a constant phase element (CPE), a single barrier of the junction CuFeO₂/electrolyte and one relaxation time of the electrical equivalent circuit.

Overcrowded naphthologs of mono-bridged tetraarylethylenes: analogs of bistricyclic aromatic enes

The naphthalogous mono-bridged tetraarylethylenes 9,9′-di-(1-naphthylmethylene)-9H-fluorene (5) and 9,9′-di-(1-naphthylmethylene)-9H-xanthene (6), analogs of bifluorenylidene (1) and bixanthenylidene (2), have been synthesized and their molecular and crystal structures have been determined. Ene 5 has been prepared by two alternative synthetic routes. The molecular structures of 5 and 6 show that each of these enes has very small twist around the central double bond, but the two naphthalene rings in both 5 and 6 are highly twisted. According to the NMR study, 5 and 6 in solution adopt conformations which are similar to those found by X-ray crystal structure analysis. The notable upfield shifts of H¹ and H⁸ (6.11 and 6.83 ppm, respectively) and H² and H⁷ (6.70 and 6.44 ppm, respectively) in 5 and 6 are due to the shielding caused by the nearly orthogonally twisted naphthalene rings. The B3LYP/6-31G(d) calculations of 5, 6, and their 2-naphthyl and phenyl analogs have been performed. In the 1-naphthyl series, the more efficient conjugation between the naphthyl substituents and the central C=C and the overcrowding due to the peri-hydrogen atoms lead to higher twists of the naphthyl groups and to lower twists of the central C=C. In the 2-naphthyl series, the opposite effects are noted. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

Luminescent Properties of Hexanuclear Molybdenum(II) Chloride Clusters Containing Thiolate Ligands

The emission spectra of a series of molybdenum(II) chloride clusters containing thiolate ligands, [Mo₆(μ₃-Cl)₈(SR)₆]²⁻ (R = Et, Bu, Ph, Bn), have been recorded. These complexes all show a broad emission at ~700 nm after excitation at 337, 400 and 410 nm. Determination of the excited state lifetimes and quantum yields of these complexes in acetonitrile reveals that (Bu₄N)₂[Mo₆(μ₃-Cl)₈(SPh)₆] displays the longest excited state lifetime of this series (26 μs at 296 K).