Proton coupled electron transfer reaction of phenols with excited state ruthenium(II) – polypyridyl complexes

The reaction of phenols with the excited state, *[Ru(bpy)₃]²⁺ (E₀ = 0.76 V) and *[Ru(H₂dcbpy)₃]²⁺, (dcbpy = 4,4′‐dicarboxy‐2,2′‐bipyridine) (E₀ = 1.55 V vs. SCE) complexes in CH₃CN has been studied by luminescence quenching technique and the quenching is dynamic. The formation of phenoxyl radical as a transient is confirmed by its characteristic absorption at 400 nm. The k_q value is highly sensitive to the change of pH of the medium and ΔG⁰ of the reaction. Based on the treatment of k_q data in terms of energetics of the reaction and pH of the medium, proton coupled electron transfer (PCET) mechanism has been proposed for the reaction. Copyright © 2010 John Wiley & Sons, Ltd.     

How glucosylation triggers physical–chemical properties of curcumin: an experimental and theoretical study

In the present study, we investigate the structures of glucosylated curcumin derivatives with DFT at B3LYP/6‐31G* level. A conformational analysis is performed in order to determine the conformational minimum (GS) and rotational transition state (TS) of curcumin derivatives and then their electronic features are evaluated. HOMO and LUMO frontier orbitals and maps of electron density potential (MEPs) are plotted and compared. In order to correlate their predicted spectroscopic properties with IR, UV–vis and NMR experimental data we extended the theoretical study on electronic properties to different solvents (H₂O, MeOH, ACN, DMSO). The main finding is that the curcuminic core maintains the same geometrical and electronic structures in all compounds miming the metal coordination capability showed by curcumin. Therefore, we may confirm that the presence of glucose does not affect the electronic properties of the derivatives. Copyright © 2010 John Wiley & Sons, Ltd.     

Pulse radiolysis studies of 2‐ and 3‐hydroxybenzyl alcohols: inhibition of dehydration of ·OH‐(hydroxybenzyl alcohols) adducts by H2PO4− ions

Reactions of ·OH/O ^.? radicals and H‐atoms as well as specific oxidants such as Cl₂^.? and N₃· radicals have been studied with 2‐ and 3‐hydroxybenzyl alcohols (2‐ and 3‐HBA) at various pH using pulse radiolysis technique. At pH 6.8, ·OH radicals were found to react quite fast with both the HBAs (k = 7.8 × 10⁹ dm³ mol^?1 s^?1 with 2‐HBA and 2 × 10⁹ dm³ mol^?1 s^?1 with 3‐HBA) mainly by adduct formation and to a minor extent by H‐abstraction from ? CH₂OH groups. ·OH‐(HBA) adduct were found to undergo decay to give phenoxyl type radicals in a pH dependent way and it was also very much dependent on buffer‐ion concentrations. It was seen that ·OH‐(2‐HBA) and ·OH‐(3‐HBA) adducts react with HPO₄^2? ions (k = 2.1 × 10⁷ and 2.8 × 10⁷ dm³ mol^?1 s^?1 at pH 6.8, respectively) giving the phenoxyl type radicals of HBAs. At the same time, this reaction is very much hindered in the presence of H₂PO ions indicating the role of phosphate ion concentration in determining the reaction pathway of ·OH adduct decay to final stable product. In the acidic region adducts were found to react with H⁺ ions. At pH 1, reaction of ·OH radicals with HBAs gave exclusively phenoxyl type radicals. Proportion of the reducing radicals formed by H‐abstraction pathway in ·OH/O ^.? reactions with HBAs was determined following electron transfer to methyl viologen. H‐atom abstraction is the major pathway in O ^.? reaction with HBAs compared to ·OH radical reaction. H‐atom reaction with 2‐ and 3‐HBA gave transient species which were found to transfer electron to methyl viologen quantitatively. Copyright © 2010 John Wiley & Sons, Ltd.     

Conformational analysis of 4,4‐dimethyl‐4‐silathiane and its S‐oxides

4,4‐Dimethyl‐4‐silathiane and its S‐oxides [n = 0 ( 1 ), 1 ( 2 ), 2 ( 3 )] were studied experimentally by variable temperature dynamic NMR spectroscopy down to 103 K and the frozen ring inversion was revealed for all three compounds. The barriers for the degenerate ring inversion in 1 and 3 were measured to be 4.8 and 5.0 kcal/mol at the coalescence temperatures of 111 and 116 K, respectively, and practically coincide with the calculated barriers of 4.60 kcal/mol in 1 and 4.46 kcal/mol in 3 . The frozen equilibrium mixture 2‐ax/2‐eq contains 37% of the 2‐ax and 63% of the 2‐eq conformer. The ring inversion barrier proved to be ca. 4.8 kcal/mol. Calculations at the B3LYP/6‐311+G(d,p) level of theory showed the 2‐ax conformer to be 0.90 kcal/mol more stable than the 2‐eq conformer in the gas phase whereas in solution the relative stability of the conformers calculated using the PCM model at the same level of theory is inverted to become 0.19 (in CHCl₃) or 0.36 kcal/mol (in DMSO) in favor of the 2‐eq conformer. The chair–chair interconversion mechanism of sulfoxide 2 includes two intermediate energetically equivalent 1,4‐twist forms and the 2,5‐boat transition state: 2‐ax (chair) ? 2 (1,4‐twist) ? [ 2 (2,5‐boat)]^≠ ? 2 (1,4‐twist) ? 2‐eq (chair). The calculated ring inversion barriers are 5.1 ( 2‐ax → 2‐eq ) and 4.2 kcal/mol ( 2‐eq → 2‐ax ) in the gas phase, and 4.03 and 4.22 kcal/mol, respectively, in chloroform. Copyright © 2011 John Wiley & Sons, Ltd.     

Adaption of a diffractometer for time‐resolved X‐ray resonant magnetic scattering

A new set‐up is presented to measure element‐selective magnetization dynamics using the ALICE chamber [Grabis et al. (2003), Rev. Sci. Instrum. 74 , 4048–4051] at the BESSY II synchrotron at the Helmholtz‐Zentrum Berlin. A magnetic‐field pulse serves as excitation, and the magnetization precession is probed by element‐selective X‐ray resonant magnetic scattering. With the use of single‐bunch‐generated X‐rays a temporal resolution well below 100 ps is reached. The ALICE diffractometer environment enables investigations of thin films, described here, multilayers and laterally structured samples in reflection or diffuse scattering geometry. The combination of the time‐resolved set‐up with a cryostat in the ALICE chamber will allow temperature‐dependent studies of precessional magnetization dynamics and of damping constants to be conducted over a large temperature range and for a large variety of systems in reflection geometry.     

Synchrotron X‐ray tests of an L‐shaped laterally graded multilayer mirror for the analyzer system of the ultra‐high‐resolution IXS spectrometer at NSLS‐II

Characterization and testing of an L‐shaped laterally graded multilayer mirror are presented. This mirror is designed as a two‐dimensional collimating optics for the analyzer system of the ultra‐high‐resolution inelastic X‐ray scattering (IXS) spectrometer at National Synchrotron Light Source II (NSLS‐II). The characterization includes point‐to‐point reflectivity measurements, lattice parameter determination and mirror metrology (figure, slope error and roughness). The synchrotron X‐ray test of the mirror was carried out reversely as a focusing device. The results show that the L‐shaped laterally graded multilayer mirror is suitable to be used, with high efficiency, for the analyzer system of the IXS spectrometer at NSLS‐II.     

Structural and ac electrical properties of a newly synthesized single phase rare earth double perovskite oxide: Ba2CeNbO6

A single phase rare earth double perovskite oxide Ba₂CeNbO₆ (BCN) is synthesized by solid-state reaction technique for the first time. The X-ray diffraction pattern of the sample at room temperature shows monoclinic structure, with the lattice parameters, a=5.9763 Å, b=5.975 Å and c=8.48 Å and β=90.04°. Impedance spectroscopy is used to study the ac electrical behavior of this material as a function of frequency (10²-10⁶ Hz) at various temperatures (30-450 °C). A relaxation is observed in the entire temperature range. Conduction mechanism is investigated by fitting the complex impedance data to Cole-Cole equation. Complex impedance plane plots show only one semicircular arc, indicating only the grain contribution of dielectric relaxation. The scaling behavior of imaginary part of electric modulus (M″) and imaginary part of electrical impedance (Z″) suggests that the relaxation describes the same mechanism at various temperatures. The frequency dependence of conductivity is interpreted in terms of the jump relaxation model and is fitted to Jonscher's power law. The values of dc conductivities extracted from the Jonscher power law varies from 2.79×10⁻⁷ to 3.5×10⁻⁵ Sm⁻¹ with the increase in temperature from 100 to 450 °C. The activation energies (0.37 eV) extracted from M″(ω) and Z″(ω) peaks are found to follow the Arrhenius law.     

Maxwell’s demon and the management of ignorance in stochastic thermodynamics

It is nearly 150 years since Maxwell challenged the validity of the second law of thermodynamics by imagining a tiny creature who could sort the molecules of a gas in such a way that would decrease entropy without exerting any work. The demon has been discussed largely using thought experiments, but it has recently become possible to exert control over nanoscale systems, just as Maxwell imagined, and the status of the second law has become a more practical matter, raising the issue of how measurements manage our ignorance in a way that can be exploited. The framework of stochastic thermodynamics extends macroscopic concepts such as heat, work, entropy and irreversibility to small systems and allows us explore the matter. Some arguments against a successful demon imply a second law that can be suspended indefinitely until we dissipate energy in order to remove the records of his operations. In contrast, under stochastic thermodynamics, the demon fails because on average, more work is performed upfront in making a measurement than can be extracted by exploiting the outcome. This requires us to exclude systems and a demon that evolve under what might be termed self-sorting dynamics, and we reflect on the constraints on control that this implies while still working within a thermodynamic framework.     

Analytic soliton solutions of cubic‐quintic Ginzburg‐Landau equation with variable nonlinearity and spectral filtering in fiber lasers

In fiber lasers, the study of the cubic‐quintic complex Ginzburg‐Landau equations (CGLE) has attracted much attention. In this paper, four families (kink solitons, gray solitons, Y‐type solitons and combined solitons) of exact soliton solutions for the variable‐coefficient cubic‐quintic CGLE are obtained via the modified Hirota method. Appropriate parameters are chosen to investigate the properties of solitons. The influences of nonlinearity and spectral filtering effect are discussed in these obtained exact soliton solutions, respectively. Methods to amplify the amplitude and compress the width of solitons are put forward. Numerical simulation with split‐step Fourier method and fourth‐order Runge‐Kutta algorithm are carried out to validate some of the analytic results. Transformation from the variable‐coefficient cubic‐quintic CGLE to the constant coefficients one is proposed. The results obtained may have certain applications in soliton control in fiber lasers, and may have guiding value in experiments in the future.