Photochemical syn-anti isomerization reactions in N2-hydroxyisocytosines--an experimental matrix isolation and theoretical study

N2-hydroxyisocytosine and 1-methyl-N2-hydroxyisocytosine were studied using a matrix isolation technique combined with infrared absorption spectroscopy. For N2-hydroxyisocytosine isolated in an Ar matrix (at 10 K), two imino-oxo isomers, one with the hydroxyimino =N-OH group directed toward the N1-H group (the form called further anti) and the second with the =N-OH group directed toward N3-H (syn), were observed in the ratio 1.4:1. The syn isomer is converted totally to the anti form after UV (lambda > 295 nm) irradiation of the matrix. A small amount of the N(3)H-hydroxy-amino tautomer of N2-hydroxyisocytosine was also detected in the matrix. This form did not react photochemically. For 1-methyl-N2-hydroxyisocytosine, only the syn form of the imino-oxo tautomer was observed after deposition of the matrix. UV (lambda > 295 nm) irradiation induced a photoreaction converting this isomer into the anti form. After 15% of the starting material had been converted into the product, a photostationary state was achieved, and no further progress of the reaction was observed. Subsequent UV irradiation (lambda > 335 nm) caused a back reaction, leading to a disappearance of the anti form and to the recovery of the initial syn isomer. All isomers were identified by comparing their experimental IR spectra with the spectra theoretically calculated at the DFT(B3LYP)/6-31G(d,p) level, where DFT is the density functional theory. Good agreement between the observed and predicted patterns of the spectral lines allowed for reliable identification. The experimental IR spectra were interpreted and discussed. The relative energies of the 12 isomers of N2-hydroxyisocytosine were calculated at the MP2/6-31G(d,p) and MP4//MP2/6-31G(d,p) levels. For six isomers of 1-methyl-N2-hydroxyisocytosine, the calculations were carried out at the MP2/6-31G(d,p) level. The anti form of the imino-oxo tautomer of N-hydroxyisocytosine and the syn form of the imino-oxo tautomer of 1-methyl-N2-hydroxyisocytosine were predicted to be the most stable.     

Cationic Porphyrin-Graphene Oxide Hybrid: Donor-Acceptor Composite for Efficient Photoinduced Electron Transfer

Non-covalent nanohybrids composed of cationic 5,10,15,20-tetra(4-trimethylammoniophenyl)porphyrin tetra(p-toluenesulfonate) (TMAP) and the graphene oxide sheets were prepared under two pH values (6.2 vs. 1.8). The TMAP molecule was positively charged, regardless of the pH value during preparation. However, protonation of the imino nitrogens increased the overall charge of the porphyrin molecule from +4 to +6 (TMAP⁴⁺ and TMAP⁶⁺). It was found that at acidic pH, interaction of TMAP⁶⁺ with GO was largely suppressed. On the other hand, results of FTIR, Raman spectroscopy, thermogravimetric analysis, atomic force microscopy (AFM) and elemental analysis confirmed effective non-covalent functionalization of graphene oxide with cationic porphyrin at pH 6.2. The TMAP⁴⁺-GO hybrids exhibited well defined structure with a monolayer of TMAP⁴⁺ on the GO sheets as confirmed by AFM. Formation of the ground-state TMAP⁴⁺-GO complex in solution was monitored by the red-shift of the porphyrin Soret absorption band. This ground-state interaction between TMAP⁴⁺ and GO is responsible for the static quenching of the porphyrin emission. Fluorescence was not detected for the nanohybrid which indicated that a very fast deactivation process had to take place. Ultrafast time-resolved transient absorption spectroscopy clearly demonstrated the occurrence of electron transfer from the photoexcited TMAP⁴⁺ singlet state to GO sheets, as proven by the formation of a porphyrin radical cation.     

Convergence theorems for adapted sequences of random sets

We consider random sets with values in a separable Banach space. We study set-valued amarts, L¹-amarts, uniform amarts and submartingales. For all these classes of random sets, we prove convergence theorems in all main modes of set convergence (weak, Wijsman, Mosco, and Hausdorff). We also prove new convergence theorems for vector-valued subpramarts and pramarts.     

Nonlinear massive spin-2 field generated by higher derivative gravity

We present a systematic exposition of the Lagrangian field theory for the massive spin-2 field generated in higher-derivative gravity upon reduction to a second-order theory by means of the appropriate Legendre transformation. It has been noticed by various authors that this nonlinear field overcomes the well-known inconsistency of the theory for a linear massive spin-2 field interacting with Einstein’s gravity. Starting from a Lagrangian quadratically depending on the Ricci tensor of the metric, we explore the two possible second-order pictures usually called “(Helmholtz-)Jordan frame” and “Einstein frame.” In spite of their mathematical equivalence, the two frames have different structural properties: in Einstein frame, the spin-2 field is minimally coupled to gravity, while in the other frame it is necessarily coupled to the curvature, without a separate kinetic term. We prove that the theory admits a unique and linearly stable ground state solution, and that the equations of motion are consistent, showing that these results can be obtained independently in either frame (each frame therefore provides a self-contained theory). The full equations of motion and the (variational) energy-momentum tensor for the spin-2 field in Einstein frame are given, and a simple but non-trivial exact solution to these equations is found. The comparison of the energy-momentum tensors for the spin-2 field in the two frames suggests that the Einstein frame is physically more acceptable. We point out that the energy-momentum tensor generated by the Lagrangian of the linearized theory is unrelated to the corresponding tensor of the full theory. It is then argued that the ghost-like nature of the nonlinear spin-2 field, found long ago in the linear approximation, may not be so harmful to classical stability issues, as has been expected.     

Evaluation by means of magneto-acoustic emission and Barkhausen effect of time and space distribution of magnetic flux density in ferromagnetic plate magnetized by a C-core

Experimental results are shown of magneto-acoustic emission (MAE) and Barkhausen effect (BE) for two ferritic steel plates of different dimensions. The paper presents preliminary results of modelling the MAE, based on the finite element method (FEM), taking into account the key role of the eddy currents. Explanations are suggested as to the effects of MAE peak maximum growth, shift, as well as the characteristic BE profiles at the bottom of the large plates.     

Evanescent light–atom interaction detected by optogalvanic effect

An evanescent light penetrating an atomic vapour near a dielectric surface could be a probe for many atom-boundary phenomena. We show the possibility of very sensitive detection of the resonant atom–light interaction near the surface by using the optogalvanic effect for an evanescent wave. We observe a narrowing of the profile of the detected atomic line, and we point out some properties of the optogalvanic effect in the evanescent wave.     

Multiplicity of nontrivial solutions for elliptic equations with nonsmooth potential and resonance at higher eigenvalues

We consider a semilinear elliptic equation with a nonsmooth, locally Lipschitz potential function (hemivariational inequality). Our hypotheses permit double resonance at infinity and at zero (double-double resonance situation). Our approach is based on the nonsmooth critical point theory for locally Lipschitz functionals and uses an abstract multiplicity result under local linking and an extension of the Castro-Lazer-Thews reduction method to a nonsmooth setting, which we develop here using tools from nonsmooth analysis.     

Reductive carbonylation of nitrobenzene over Pd/Fe/I2/Py and Pd/C/Fe/I2/Py catalytic systems

A simple catalytic system containing metallic palladium, iron and iodine has been shown to be very active in the carbonylation of nitrobenzene to carbamate. The influence of the components of the catalytic system studied on its selectivity and activity has been established. It has been found that the catalytic activity of palladium supported on carbon (using both lignite coal and bituminous coal) was not lower than the activity of metallic palladium. This revised version was published online in August 2006 with corrections to the Cover Date.     

Direct and reverse energy transport in systems of monomers and imperfect traps: Monte Carlo simulations

A Monte Carlo simulation of the concentration dependence of the fluorescence quantum yield _M and emission anisotropyr _M of a system containing dye molecules in the form of monomers M and clusters T (statistical pairs and trimers) playing the role of the imperfect traps for nonradiative excitation energy transfer (NET) has been carried out. The simulation has been made for determined values of Förster critical distancesR ₀ ^MM andR ₀ ^MT and for several values ofR ₀ ^TM andR ₀ ^TT , assuming that the energy may be transferred from M^* to T as well as from T^* to M (reverse nonradiative energy transfer, RNET). It was shown that the RNET process in the range of high concentrations may strongly change the values ofr _M as well as those of _M. For emission anisotropyr _M an effect of repolarization was observed which decreases rapidly with increasingR ₀ ^TM andR ₀ ^TT . A very good agreement between the simulation results of _M and the theoretical model with no adjustable parameters was found. In the model, the RNET process and influence of correlation between active molecules on energy migration among monomers were taken into account.