Separation of quadrupolar and paramagnetic shift interactions with TOP-STMAS/MQMAS in solid-state lighting phosphors

A new approach for processing satellite-transition magic-angle spinning (STMAS) and multiple-quantum magic-angle spinning (MQMAS) data, based on the two-dimensional one-pulse (TOP) method, which separates the second-rank quadrupolar anisotropy and paramagnetic shift interactions via a double shearing transformation, is described. This method is particularly relevant in paramagnetic systems, where substantial inhomogeneous broadening may broaden the lineshapes. Furthermore, it possesses an advantage over the conventional processing of MQMAS and STMAS spectra because it overcomes the limitation on the spectral width in the indirect dimension imposed by rotor synchronization of the sampling interval. This method was applied experimentally to the Al solid-state nuclear magnetic resonance of a series of yttrium aluminum garnets (YAGs) doped with different lanthanide ions, from which the quadrupolar parameters of paramagnetically shifted and bulk unshifted sites were extracted. These parameters were then compared with density functional theory calculations, which permitted a better understanding of the local structure of Ln substituent ions in the YAG lattice.     

The largest connected component in a random mapping

A random mapping (T; q) of a finite set V = {1, 2,…,n} into itself assigns independently to each i ? V its unique image j = TT(i)E V with probability q for i = j and with probability $ \frac{{1 - q}}{{n - 1}} $ for j ≠ i. The purpose of the article is to determine the asymptotic behaviour of the size of the largest connected component of the random digraph G_T(q) representing thes mapping as n–x, regarding all possible values of the parameter q = q(n). © 1994 John Wiley & Sons, Inc.     

Modulation of the proton transfer rate by excitation photons

The effect of the exciting photon energy on the excited state proton transfer in a dye with dual fluorescence—FET (4′-diethylamino)-3-hydroxyflavone)—is studied. The steady-state fluorescence spectra are studied upon selective excitation by photons with different energies in the region of the main absorption band, as well as at its long-wavelength wing, in the temperature range of 2–30°C. It is found that, at all temperatures, the ratio of the integral emission of the normal and tautomeric forms, which are observed at 480 and 570 nm, respectively, depends on the excitation wavelength; namely, this ratio noticeably decreases with increasing excitation wavelength in the region of the main absorption band and its long-wavelength wing at 390–440 nm, and the rate of this decrease depends on temperature. In the same region, the long-wavelength excitation effect, which is atypical for inviscid solvents at room temperature, is observed; i.e., a short-wavelength emission band is bathochromically shifted by 6–15 nm depending on temperature. This spectral shift is directly related to the inhomogeneous broadening of the electronic spectra of the normal FET form, which is very large due to a considerable (>10 D) difference in the dye dipole moments. Most probably, the excitation creates the possibility of emission from nonrelaxed nonequilibrium orientational sublevels because their lifetime becomes shorter due to the proton transfer reaction, the rate of which in acetonitrile is comparable with the rate of intermolecular orientational relaxation. It is proposed to explain these dependences using energy diagram taking into account the dependence of the free energy on the orientational polarization of the solvent.     

Ergodic and Mixing Probability Measures on [SIN] Groups

We prove that the concepts of completely mixing, mixing, and weakly mixing probability measures on a locally compact group in the class [SIN] are mutually equivalent. A probability measure on such a group is completely mixing if and only if it is ergodic and aperiodic. For measures that are not necessarily aperiodic ergodicity is shown to be equivalent to a mixing-like property which we call almost mixing. Some results on when a probability measure on a [SIN] group is ergodic are also developed. Our methods are based on the theory of boundaries of random walks.     

A poisson formula for solvable Lie groups

Given a probability measure μ on a locally compact second countable groupG the space of bounded μ-harmonic functions can be identified withL ^∞(η, α) where (η, α) is a BorelG-space with a σ-finite quasiinvariant measure α. Our goal is to show that when μ is an arbitrary spread out probability measure on a connected solvable Lie groupG then the μ-boundary (η, α) is a contractive homogeneous space ofG. Our approach is based on a study of a class of strongly approximately transitive (SAT) actions ofG. A BorelG-space η with a σ-finite quasiinvariant measure α is called SAT if it admits a probability measurev≪α, such that for every Borel set A with α(A)≠0 and every ε>0 there existsg∈G with ν(gA)>1−ε. Every μ-boundary is a standard SATG-space. We show that for a connected solvable Lie group every standard SATG-space is transitive, characterize subgroupsH⊆G such that the homogeneous spaceG/H is SAT, and establish that the following conditions are equivalent forG/H: (a)G/H is SAT; (b)G/H is contractive; (c)G/H is an equivariant image of a μ-boundary.     

Dissipation of Convolution Powers in a Metric Group

In contrast to what is known about probability measures on locally compact groups, a metric group G can support a probability measure μ which is not carried on a compact subgroup but for which there exists a compact subset C⊆G such that the sequence μ ⁿ (C) fails to converge to zero as n tends to ∞. A noncompact metric group can also support a probability measure μ such that supp μ=G and the concentration functions of μ do not converge to zero. We derive a number of conditions which guarantee that the concentration functions in a metric group G converge to zero, and obtain a sufficient and necessary condition in order that a probability measure μ on G satisfy lim  _n→∞ μ ⁿ (C)=0 for every compact subset C⊆G. Supported by an NSERC Grant.     

MicroRNA Delivery by Graphene-Based Complexes into Glioblastoma Cells

Glioblastoma (GBM) is the most common primary and aggressive tumour in brain cancer. Novel therapies, despite achievements in chemotherapy, radiation and surgical techniques, are needed to improve the treatment of GBM tumours and extend patients’ survival. Gene delivery therapy mostly uses the viral vector, which causes serious adverse events in gene therapy. Graphene-based complexes can reduce the potential side effect of viral carries, with high efficiency of microRNA (miRNA) or antisense miRNA delivery to GBM cells. The objective of this study was to use graphene-based complexes to induce deregulation of miRNA level in GBM cancer cells and to regulate the selected gene expression involved in apoptosis. The complexes were characterised by Fourier transform infrared spectroscopy (FTIR), scanning transmission electron microscopy and zeta potential. The efficiency of miRNA delivery to the cancer cells was analysed by flow cytometry. The effect of the anticancer activity of graphene-based complexes functionalised by the miRNA sequence was analysed using 2,3-bis-(2-methoxy-4-nitro-5-sulfophenyl)-2H-tetrazolium-5-carboxyanilide salt (XTT) assays at the gene expression level. The results partly explain the mechanisms of miRNA deregulation stress, which is affected by graphene-based complexes together with the forced transport of mimic miR-124, miR-137 and antisense miR-21, -221 and -222 as an anticancer supportive therapy.