Syntheses,characterization of and studies on the electrochemical behaviour of ferrocenyl dithiophosphonates and 4-methoxyphenyl dithiophosphonates

Some 1,3-dithiadiphosphetane 2,4-disulfides (X₂P₂S₄, X: Fc, FcLR; X: CH₃O?C₆H₄?, LR) were allowed to react with alcohols to obtain dithiophosphonic acids (X(OR)PS₂H). These were converted to the corresponding ammonium salts. The salts were of the structures [Fc(OR)PS₂]^?[NH₄]⁺, R: 3-methyl-1-butyl- for I; 1-phenyl-1-propyl- for II; 3-pentyl- for III; 3-phenyl-1-propyl- for IV and [CH₃O?C₆H₄(OR)PS₂]^?[NH₄]⁺, R: 3-methyl-1-butyl- for V and 1-phenyl-1-propyl- for VI. To the best of our knowledge, all the compounds except V were prepared for the first time.

The compounds synthesized were characterized by elemental analysis, NMR (¹H, ¹³C, ³¹P), MS, FTIR, and Raman spectroscopies. Electrochemical behaviors of I–VI at disposable pencil graphite electrode (PGE) were investigated by using cyclic voltammetry (CV) and square-wave voltammetry (SWV). Adsorption and diffusion patterns of all the compounds on the PGE were also studied.

Two electroactive groups were identified in the compounds I–IV and only one in V and VI. The ferrocenyl groups of I-IV were oxidized at around 0.4 V. The same compounds display a second, more intense CV band at 0.8 V. The corresponding band for the compounds V–VI appears at around 0.6 V with a much weaker intensity. It is suggested that the ferrocenyl group introduced into the structures stabilizes the radical species formed as the product of the oxidation of the dithiophosphonato group.     

Solvent,substituent, and dimerization effects on the ring-opening mechanisms of monosilacyclopropylidenoids: a theoretical study

Density functional theory and ab initio computations elucidated the ring-opening of substituted (R = –CF₃, –CN, –CH₃, –H, –NH₂, –OCH₃, –OH, –SiH₃) 1-bromo–1-lithiosilirane 1 and 2-bromo–2-lithiosilirane 2 to LiBr complexes of 2-silaallene and 1-silaallene, respectively. Formally, two competitive pathways can be considered. The ring-opening reaction can take place through a concerted manner via TS3. Alternatively, the reaction may proceed in a stepwise fashion with the intermediacy of a free silacyclopropylidene–LiBr complex 7. In both cases, the position of the substituents determines the kinetic of the reactions. The structures with an electron-donating group are generally unstable, whereas the silacyclopropylidenoids bearing electron-withdrawing substituents are particularly stable species. Here, we propose the ring-opening of 5a–h to corresponding LiBr complexes of 2-silaallenes can proceed in both concerted and stepwise mechanism except for –H, –CH₃, and –SiH₃. The obtained activation energies for the ring-openings of 5a–h to related 2-silaallenes are too high for a reaction at room temperature with up to 61.4 kcal/mol. In contrast, the activation energy barriers for the isomerization of 6a–h to the LiBr complexes of 1-silaallenes was determined to be relatively low at the B3LYP/6-31+G(d,p), M06/6-31+G(d,p), and MP2/6-31+G(d,p) levels. Moreover, we have also investigated the solvent effect on the unsubstituted models using both implicit and explicit solvation models. The energy barriers of the solvated models are found to be slightly higher than the results of gas phase calculations. Additionally, the ring-opening of dimer 6 (6–Dim) is also calculated for the ring-opening mechanism with the energy barrier of 3.7 kcal/mol at B3LYP/6-31+G(d,p) level of theory.     

Hydrogen generation by hangman metalloporphyrins

A cobalt(II) hangman porphyrin with a xanthene backbone and a carboxylic acid hanging group catalyzes the electrochemical production of hydrogen from benzoic and tosic acid in acetonitrile solutions. We show that Co(II)H is exclusively involved in the generation of H(2) from weak acids. In a stronger acid, a Co(III)H species is observed electrochemically, but it still needs to be further reduced to Co(II)H before H(2) generation occurs. Overpotentials for H(2) generation are lowered as a result of the hangman effect.     

LC-MS based quantification of 2'-ribosylated nucleosides Ar(p) and Gr(p) in tRNA

RNA nucleosides are often naturally modified into complex non-canonical structures with key biological functions. Here we report LC-MS quantification of the Ar(p) and Gr(p) 2'-ribosylated nucleosides in tRNA using deuterium labelled standards, and the first detection of Gr(p) in complex fungi.     

Interstitialcy diffusion of oxygen in tetragonal La2CoO(4+δ)

We report on the mechanism and energy barrier for oxygen diffusion in tetragonal La(2)CoO(4+δ). The first principles-based calculations in the Density Functional Theory (DFT) formalism were performed to precisely describe the dominant migration paths for the interstitial oxygen atom in La(2)CoO(4+δ). Atomistic simulations using molecular dynamics (MD) were performed to quantify the temperature dependent collective diffusivity, and to enable a comparison of the diffusion barriers found from the force field-based simulations to those obtained from the first principles-based calculations. Both techniques consistently predict that oxygen migrates dominantly via an interstitialcy mechanism. The single interstitialcy migration path involves the removal of an apical lattice oxygen atom out from the LaO-plane and placing it into the nearest available interstitial site, whilst the original interstitial replaces the displaced apical oxygen on the LaO-plane. The facile migration of the interstitial oxygen in this path is enabled by the cooperative titling-untilting of the CoO(6) octahedron. DFT calculations indicate that this process has an activation energy significantly lower than that of the direct interstitial site exchange mechanism. For 800-1000 K, the MD diffusivities are consistent with the available experimental data within one order of magnitude. The DFT- and the MD-predictions suggest that the diffusion barrier for the interstitialcy mechanism is within 0.31-0.80 eV. The identified migration path, activation energies and diffusivities, and the associated uncertainties are discussed in the context of the previous experimental and theoretical results from the related Ruddlesden-Popper structures.     

Synthesis and characterization of epoxy resins containing imine group and their curing processes with aromatic diamine

The epoxy resins containing imine bonding were prepared from hydroxyl substituted Schiff base monomers in two steps. At the first step, hydroxyl substituted Schiff base monomers were synthesized via condensation reaction. At the second step, epoxy resins were synthesized from the reaction between Schiff base monomers and epichlorohydrine (EPC). Then curing processes of epoxy resins were achieved by p-phenylenediamine compound. The structures of resulting compounds were confirmed by FT-IR, UV-Vis and ¹H-NMR. TG-DTA and DSC measurements were performed for thermal characterizations of the compounds. Chemical resistances of the cured epoxy-amine systems were determined for coating applications in acidic, alkaline and organic solvents. HCl (10%, aqueous solution), NaOH (10%, aqueous solution), DMSO, DMF, N-methylpyrrolidone, ethanol, THF and acetone were used for corrosion tests. Chemical resistance data of the synthesized epoxy resins demonstrated that they have good chemical resistance against various acid, alkaline and common organic solvents. Surface morphologies of epoxy resin and the cured epoxy resin were determined with scanning electron microscopy (SEM) measurements. Also, optical band gap (E_g) values of Schiff base monomers and epoxy resins were calculated from UV-Vis measurements.     

Summary of the CMS potential for the Higgs boson discovery

The European Physical Journal C - This work summarizes the studies for the Higgs boson searches in CMS at the LHC collider. The main discovery channels are presented and the potential is given for...     

Optimum thickness distribution of unconstrained viscoelastic damping layer treatments for plates

This paper concerns the optimum thickness distribution of unconstrained viscoelastic damping layer treatments for plates. The system loss factor is expressed in terms of the mechanical properties of the plate and damping layer and the layer/plate thickness ratio. Optimum distributions of the thickness ratio that maximize the system loss factor are obtained through sequential unconstrained minimization techniques. Results are presented for both simply-supported and edge-fixed rectangular plates with aspect ratios of 1·0 to 4·0. These results indicate that the system loss factor can be increased by as much as 100%, or more, by optimizing the thickness distribution of the damping treatment. Also revealed are the regions of the plate where added damping treatments are most effective.