Positivity of Lyapunov Exponents for a Continuous Matrix-Valued Anderson Model

We study a continuous matrix-valued Anderson-type model. Both leading Lyapunov exponents of this model are proved to be positive and distinct for all energies in (2, +∞) except those in a discrete set, which leads to absence of absolutely continuous spectrum in (2, +∞). This result is an improvement of a previous result with Stolz. The methods, based upon a result by Breuillard and Gelander on dense subgroups in semisimple Lie groups, and a criterion by Goldsheid and Margulis, allow for singular Bernoulli distributions.      

Assignment of the EPR spectrum of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) superoxide spin adduct

[structure: see text] Spin trapping consists of using a nitrone or a nitroso compound to "trap" an unstable free radical as a long-lived nitroxide that can be characterized by electron paramagnetic resonance (EPR) spectroscopy. The formation of DMPO-OOH, the spin adduct resulting from trapping superoxide (O(2)(*)(-)) with 5,5-dimethyl-1-pyrroline N-oxide (DMPO), has been exploited to detect the generation of superoxide in a wide variety of biological and chemical systems. The 12-line EPR spectrum of DMPO-OOH has been either reported or mentioned in more than a thousand papers. It has been interpreted as resulting from the following couplings: A(N) approximately 1.42 mT, A(H)beta approximately 1.134 mT, and A(H)gamma(1H) approximately 0.125 mT. However, the DMPO-OOH EPR spectrum has an asymmetry that cannot be reproduced when the spectrum is calculated considering a single species. Recently, it was proposed that the 0.125 mT splitting was misassigned and actually results from the superimposition of two individual EPR spectra associated with different conformers of DMPO-OOH. We have prepared 5,5-dimethyl-[3,3-(2)H(2)]-1-pyrroline N-oxide (DMPO-d(2)), and we showed that the EPR spectrum of the corresponding superoxide spin adduct is composed of only six lines, in agreement with the assignment of the 0.125 mT splitting to a gamma-splitting from a hydrogen atom bonded to carbon 3 of DMPO. This result was supported by DFT calculations including water solvation, and the asymmetry of the DMPO-OOH EPR spectrum was nicely reproduced assuming a chemical exchange between two conformers.     

Properties of block and graft copolymers of polybutadiene with small complexed poly(4-vinylpyridine) segments

Various diblocks, triblocks and a graft copolymer of butadiene with 4-vinylpyridine short blocks have been prepared. They were complexed with ZnCl₂ to give ionomer-like materials. For all copolymers, the T_g of the elastomeric block (?84°C to ?91°C) was unchanged by complexation. For all diblocks and triblocks with short blocks (DP _n ～ 3) the storage modulus was only slightly increased by comparison with uncomplexed materials. For the graft copolymer even with short blocks the material is less sensitive to temperature after complexation. For triblocks, when the DP _n of the vinylpyridine blocks was high enough (15 units), complexes were associated in multiplets of large size and the elastomeric properties were retained up to 200°C.     

Exact exponent for the number of persistent spins in the zero-temperature dynamics of the one-dimensional Potts model

For the zero-temperature Glauber dynamics of theq-state Potts model, the fractionr(q, t) of spins which never flip up to timet decays like a power lawr(q, t)t ^–(q) when the initial condition is random. By mapping the problem onto an exactly soluble one-species coagulation model (A+AA) or alternatively by transforming the problem into a free-fermion model, we obtain the exact expression of (q) for all values ofq. The exponent (q) is in general irrational, (3)=0.53795082..., (4)=0.63151575..., ..., with the exception ofq=2 andq=, for which (2)=3/8 and ()=1.     

Modified dispersive liquid-liquid microextraction for pre-concentration of benzene, toluene, ethylbenzene and xylenes prior to their determination by GC

We have developed a modified method for the extraction and preconcentration of benzene, toluene, ethylbenzene and xylenes (BTEX) in aqueous samples. It based on dispersive liquid-liquid microextraction along with solidification of floating organic microdrops. The dispersion of microvolumes of an extracting solvent into the aqueous occurs without dispersive solvent. Various parameters have been optimized. BTEX were quantified via GC with FID detection. Under optimized conditions, the preconcentration factors range from 301 to 514, extraction efficiencies from 60 to 103 %, repeatabilities from 2.2 to 4.1 %, and intermediate precisions from 3.5 to 7.0 %. The relative recovery for each analyte in water samples at three spiking levels is >85.6 %, with a relative standard deviation of <7.4 %.

Modelling interaction between ammonia and nitric oxide molecules and aquaporins

Aquaporin is a family of small membrane-proteins that are capable of transporting nano-sized materials. In the present paper, we investigate the structure of these channels and provide information about the mechanism of individual molecules being encapsulated into aquaglyceroporin (GlpF) and aquaporin-1 (AQP1) channels by calculating the potential energy. In particular, we presents a mathematical model to determine the total potential energy for the interaction of the ammonia and nitric oxide molecules and different aquaporin channels which we assume to have a symmetrical cylindrical structure. We propose to describe these interactions in two steps. Firstly, we model the nitrogen atom as a discrete point and secondly, we model the three hydrogen atoms on the surface of a sphere of a certain radius. Then, we find the total potential energy by summing these interactions. Next, by considering the nitric oxide molecule as two discrete atoms uniformly distributed interacting with GlpF and AQP1 channels then gathering all pairs of interaction to determine the potential energy. Our results show that the ammonia and nitric oxide molecules can be encapsulated into both GlpF and AQP1 channels.