Pourbaix diagrams in weakly coupled systems: a case study involving acridinol and phenanthridinol pseudobases

The thermodynamics of proton‐coupled electron transfer (PCET) in weakly coupled organic pseudobases was investigated using 2,7‐dimethyl‐9‐hydroxy‐9‐phenyl‐10‐tolyl‐9,10‐dihydroacridine (AcrOH) and 6‐phenylphenanthridinol (PheOH) as model compounds. Pourbaix diagrams for two model compounds were constructed using the oxidation potentials and the pK_a values obtained, respectively, from cyclic voltammetry and photometric titrations. Our comparative study reveals the importance of having the redox active –N center closer to –OH functionality on the thermodynamics of PCET process: PheOH exhibits a wider range of pH values (pH = 2.8 to 13.3) in which both the alcohol and the corresponding alkoxy radical are expected to coexist in solution. This result indicates that a concerted mechanism is more likely to be discovered in pseudobases analogous to PheOH. The thermochemical data also indicate that the concerted PCET mechanism cannot be achieved if water is used as the proton acceptor: assuming the pK_a of hydronium ions as ?1.7, the PCET involving PheOH or AcrOH as proton/electron donors and water as the proton acceptor is expected to follow the stepwise ET/PT mechanism. Copyright © 2015 John Wiley & Sons, Ltd.     

Electron delocalization and dimerization in solid C59N doped C60 fullerene

Electron spin resonance and ab initio electronic structure calculations show an intricate relation between molecular rotation and chemical bonding in the dilute solid solution. The unpaired electron of C59N is delocalized over several C60 molecules above 700 K, while at lower temperatures it remains localized within short range. The data suggest that below 350 K rigid C59N-C60 heterodimers are formed in thermodynamic equilibrium with dissociated rotating molecules. The structural fluctuations between heterodimers and dissociated molecules are accompanied by simultaneous electron spin transfer between C60 and C59N molecules. The calculation confirms that in the C59N-C60 heterodimer the spin density resides mostly on the C60 moiety, while it is almost entirely on C59N in the dissociated case.     

Electric-field control of exchange bias in multiferroic epitaxial heterostructures

The magnetic exchange between epitaxial thin films of the multiferroic (antiferromagnetic and ferroelectric) hexagonal YMnO3 oxide and a soft ferromagnetic (FM) layer is used to couple the magnetic response of the FM layer to the magnetic state of the antiferromagnetic one. We will show that biasing the ferroelectric YMnO3 layer by an electric field allows control of the magnetic exchange bias and subsequently the magnetotransport properties of the FM layer. This finding may contribute to paving the way towards a new generation of electric-field controlled spintronic devices.     

Conductivity and field and current distributions in a two-component system composed of regular triangles

The problem of the effective conductivity and the distributions of a field and currents is analyzed in a regular two-component system composed of regular triangles. An efficient solution method is developed that admits a generalization to multicomponent systems.     

Ultrasound promoted synthesis of thioesters from 2-mercaptobenzoxa(thia)zoles

An ultrasound-enhanced method has been developed for the synthesis of a variety of thioesters from benzoyl chlorides and 2-mercaptobenzoxa(thia)zoles. Applying this methodology, 14 compounds were synthesized in excellent yields.     

Model study on steady heat capacity in driven stochastic systems

We explore two- and three-state Markov models driven out of thermal equilibrium by non-potential forces, to demonstrate basic properties of the steady heat capacity based on the concept of quasistatic excess heat. It is shown that large enough driving forces can make the steady heat capacity negative. For both the low- and high-temperature regimes we propose an approximative thermodynamic scheme in terms of “dynamically renormalized” effective energy levels.     

Analysis of spectral properties of acoustic noise produced during magnetic resonance imaging

Magnetic resonance imaging (MRI) technique enables non-invasive analysis of the human vocal tract during phonation. Creation of MR images of the vocal tract is accompanied by simultaneous recording of the produced speech. The paper analyzes and compares spectral properties of an acoustical noise produced by mechanical vibration of the gradient coils during scanning in the open-air MRI equipment working in a weak magnetic field with low B₀ up to 0.2 T. This noise exhibits harmonic character, so it is suitable to analyze its properties in the spectral domain. Obtained results of spectral analysis will be used to devise a new cepstral-based filtering method for noise suppression of recorded speech.     

Galvanomagnetic and thermoelectric properties of multicomponent n-type solid solutions based on Bi and Sb chalcogenides

The galvanomagnetic and thermoelectric properties of n-Bi_2-x Sb_xTe_3-y-z Se_yS_z multicomponent solid solutions with atomic substitutions (Sb → Bi; Se, S → Te) are studied. The principal components of the effective mass tensor (m ₁, m ₂, m ₃) for the isotropic mechanism of charge carrier scattering are determined within a many-valley model of the energy spectrum for compositions 0.08 ≤ x ≤ 0.4 and 0.06 ≤ y = z ≤ 0.15. The effect of a variation in the parameters of the constant-energy surface on the thermoelectric efficiency is analyzed for different compositions and carrier concentrations in solid solutions.     

Low-loss multilayered metamaterial exhibiting a negative index of refraction at visible wavelengths

We experimentally demonstrate a low-loss multilayered metamaterial exhibiting a double-negative refractive index in the visible spectral range. To this end, we exploit a second-order magnetic resonance of the so-called fishnet structure. The low-loss nature of the employed magnetic resonance, together with the effect of the interacting adjacent layers, results in a figure of merit as high as 3.34. A wide spectral range of negative index is achieved, covering the wavelength region between 620 and 806 nm with only two different designs.