Diffusion of Gold Nanoparticles in Inverse Opals Probed by Heterodyne Dynamic Light Scattering

The diffusive behavior of nanoparticles inside porous materials is attracting a lot of interest in the context of understanding, modeling, and optimization of many technical processes. A very powerful technique for characterizing the diffusive behavior of particles in free media is dynamic light scattering (DLS). The applicability of the method in porous media is considered, however, to be rather difficult due to the presence of multiple sources of scattering. In contrast to most of the previous approaches, the DLS method was applied without ensuring matching refractive indices of solvent and porous matrix in the present study. To test the capabilities of the method, the diffusion of spherical gold nanoparticles within the interconnected, periodic nanopores of inverse opals was analyzed. Despite the complexity of this system, which involves many interfaces and different refractive indices, a clear signal related to the motion of particles inside the porous media was obtained. As expected, the diffusive process inside the porous sample slowed down compared to the particle diffusion in free media. The obtained effective diffusion coefficients were found to be wave vector-dependent. They increased linearly with increasing spatial extension of the probed particle concentration fluctuations. On average, the slowing-down factor measured in this work agrees within combined uncertainties with literature data.

     

Ohkuma Structures

The construction and characterization by T. Ohkuma of a chain whose automorphism group acts uniquely transitively is extended in this article to analogues for circularly ordered sets and betweenness chains.     

Global statistical predictor model for characteristic adsorption energy of organic vapors-solid interaction: use in dynamic process simulation

Adsorption of Volatile Organic Compounds (VOCs) is one of the best remediation techniques for controlling industrial air pollution. In this paper, a quantitative predictor model for the characteristic adsorption energy (E) of the Dubinin-Radushkevich (DR) isotherm model has been established with R(2) value of 0.94. A predictor model for characteristic adsorption energy (E) has been established by using Multiple Linear Regression (MLR) analysis in a statistical package MINITAB. The experimental value of characteristic adsorption energy was computed by modeling the isotherm equilibrium data (which contain 120 isotherms involving five VOCs and eight activated carbons at 293, 313, 333, and 353 K) with the Gauss-Newton method in a statistical package R-STAT. The MLR model has been validated with the experimental equilibrium isotherm data points, and it will be implemented in the dynamic adsorption simulation model PROSIM. By implementing this model, it predicts an enormous range of 1200 isotherm equilibrium coefficients of DR model at different temperatures such as 293, 313, 333, and 353K (each isotherm has 10 equilibrium points by changing the concentration) just by a simple MLR characteristic energy model without any experiments.     

Beta-delayed neutron radioactivity of15B

The new beta-delayed neutron emitter¹⁵B has been observed. The measured half-life is 11 ms ±1 ms and limits have been set on other decay channels: P_0n<5%, P_2n<1.5%. The beta emitter¹²Be has been separated, unambiguously identified, and its half-life has been measured to be 24±1 ms.     

Uniqueness of the group operation on the lattice of order-automorphisms of the real line

A(R) is the lattice-ordered group (l-group) of all order-automorphisms of the real lineR, with the usual pointwise order and “of course” with composition as the group operation. In fact, what other choices are there for a group operation having the same identity that would give anl-group? Composition in the reverse order would work. But there are no other choices — the group operation can be recognized in the lattice. Several classes of abelianl-groups having a unique group operation have been found by Conrad and Darnel, but this is the first non-abelian example having the minimum of two group operations. “Conversely”, Holland has shown that for the groupA(R) under composition, the only lattice orderings yielding anl-group are the pointwise order and its dual. These results also hold for the rational lineQ.     

EPR and solid-state NMR studies of poly(dicarbon monofluoride) (C2F)n

Poly(dicarbon monofluoride) (C2F)n was studied by electron paramagnetic resonance (EPR) and solid-state nuclear magnetic resonance (NMR). The effects of physisorbed oxygen on the EPR and NMR relaxation were underlined and extrapolated to poly(carbon monofluoride) (CF)n and semi-covalent graphite fluoride prepared at room temperature. Physisorbed oxygen molecules are shown to be an important mechanism of both electronic and nuclear relaxations, resulting in apparent spin-lattice relaxation time and line width during NMR and EPR measurements, respectively. The effect of paramagnetic centers on the 19F spin-lattice relaxation was underlined in accordance with the high electron spin density determined by EPR. 19F magic angle spinning (MAS) NMR, 13C MAS NMR, and 13C MAS NMR with 19F to 13C cross polarization (CP) underline the presence of two types of carbon atoms, both sp3 hybridized: some covalently bonded to fluorine and the others linked exclusively to carbon atoms. Finally, a C-F bond length of 0.138 +/- 0.002 nm has been determined thanks to the re-introduction of dipolar coupling using cross polarization.     

Solid-state F and C NMR of room temperature fluorinated graphite and samples thermally treated under fluorine: Low-field and high-resolution studies

Room temperature graphite fluorides consisting of raw material and samples post-treated in pure fluorine atmosphere in the temperature range 100-500 °C have been studied by solid-state NMR. Several NMR approaches have been used, both high and low-field ¹⁹F, ¹⁹F MAS and ¹³C MAS with ¹⁹F to ¹³C cross polarization. The modifications, in the graphitic lattice, of the catalytic iodine fluorides products have been examined. A transformation of the C-F bond character from semi-ionic to covalent has been found to occur at a post-treatment temperature close to 400 °C. It is shown that covalency increases with temperature.     

Undecidability of automorphism groups

We give a simple (and easy to apply) technique that gives the undecidability of the theory of many automorphism groups: Let G be a group of automorphisms of a structure. Suppose that is not the identity and has no non-singleton finite orbits. If the centraliser of g is transitive on the support of g and satisfies a further technical condition, then the subgroup generated by g is equal to the double centraliser of g. Thus if G contains such an element g that is conjugate to all its positive powers, then one can interpret addition and multiplication of natural numbers in the theory of G using the parameter g; consequently, G has undecidable theory. Received: 9 October 2000 / in final form: 2 October 2001 / Published online: 29 April 2002     

Solid-state NMR study of the post-fluorination of (C2.5F)n fluorine-GIC

The conversion of (C2.5F)n fluorine-graphite intercalation compounds (GIC) into covalent graphite fluoride during a post-treatment in pure F2 gas is studied by solid-state NMR. First, a careful characterization of the starting material is performed; in particular, for the first time for fluorinated carbons, two-dimensional 19F--> 13C cross-polarization wide-line separation (CP-WISE) experiments were carried out. This completes the classical NMR data such as 19F and 13C chemical shifts, quantitative 13C solid echo, and C-F bond length measurements, which were estimated by dipolar recoupling using inverse CP MAS. The data of the raw (C2.5F)n and of the samples post-fluorinated at 350, 450, and 550 degrees C were compared to investigate the C-F bonding as a function of the treatment temperature. The C-F bonding is discussed taking into account a hyperconjugation of the C-F bonds with neighboring unfluorinated carbon atoms.