Fundamental reactions in TiO2 nanocrystallite aqueous solutions studied by pulse radiolysis

Reactions of the hydrated electron, H atoms, 2-propanol, and methanol radicals with the TiO₂ nano-particles have been studied either directly or by competition kinetics. The radicals were produced by radiolysis of 2-propanol, t-butanol, or methanol aqueous solutions in acid pH's. The reactions involve electron injection to the conduction band. As expected, the t-butanol radical is inert towards TiO₂ under our conditions, while the other reducing radicals react with TiO₂. The reactivity decreases in the order: e_aq⁻>H>CH₃COHCH₃>CH₂OH. Two TiO₂ nanocrystallite sizes, with average diameters of 1.0 and 4.7 nm were compared. For equal concentrations (in terms of TiO₂ molecules), the rate of electron injection shows relatively little dependency on particle size. The rates of interfacial electron transfer and transfer coefficient are also reported.     

Fairness in Scheduling

On-line machine scheduling has been studied extensively, but the fundamental issue of fairness in scheduling is still mostly open. In this paper we explore the issue in settings where there are long-lived processes which should be repeatedly scheduled for various tasks throughout the lifetime of a system. For any such instance we develop a notion ofdesiredload of a process, which is a function of the tasks it participates in. Theunfairnessof a system is the maximum, taken over all processes, of the difference between the desired load and the actual load.An example of such a setting is thecarpool problemsuggested by Fagin and Williams [IBM Journal of Research and Development27(2) (1983), 133–139]. In this problem, a set ofnpeople form a carpool. On each day a subset of the people arrive and one of them is designated as the driver. A scheduling rule is required so that the driver will be determined in a “fair” way.We investigate this problem under various assumptions on the input distribution. We also show that the carpool problems can capture several other problems of fairness in scheduling.     

Comparison of dynamical heterogeneity in hard-sphere and attractive glass formers

Using molecular dynamics simulations, we have determined that the nature of dynamical heterogeneity in jammed liquids is very sensitive to short-ranged attractions. Weakly attractive systems differ little from dense hard-sphere and Lennard-Jones fluids. Particle motion is punctuated and tends to proceed in steps of roughly a single particle diameter. Both of these basic features change in the presence of appreciable short-ranged attractions. Transient periods of particle mobility and immobility cannot be discerned at intermediate attraction strength, for which structural relaxation is greatly enhanced. Strong attractions, known to dramatically inhibit relaxation, restore bimodality of particle motion. But in this regime, transiently mobile particles move in steps that are significantly more biased toward large displacements than those in the case of weak attractions. This modified feature of dynamical heterogeneity, which cannot be captured by conventional mode coupling theory, verifies recent predictions from a model of spatially correlated facilitating defects.     

Fluorimetric Determination of Histamine in Fish Using Micellar Media and Fluorescamine as Labelling Reagent

An analytical method based on the use of fluorescamine to produce a fluorescent derivative with histamine and combined with micellar-enhanced fluorescence detection of the formed complex is developed for the sensitive and rapid determination of histamine in fishes. The fluorescence properties of the obtained complex in water and micellar solutions of sodium dodecyl sulfate (SDS), cetyltrimethylammonium chloride (CTAC) and brij-700 are reported. Physicochemical variables influencing the sensitivity of the method (pH, micellar, fluorescamine and NaCl relative concentrations) have been optimized. The stability of the formed complex, as shown by kinetic study, depends on the pH of the solution. Linear calibration curves allowing an effective histamine determination were established with large linear dynamic range (LDR), and low limits of detection (LOD) between 0.5 and 33 ng mL⁻¹, according to the solvent. Application to the analysis of fish samples (sardines) yielded satisfactory results. The method seems to be suitable for environmental fish quality control. Presented in part, at the 39th IUPAC Congress and the 86th Conference of the Canadian Society for Chemistry, August, 10–15, 2003, Ottawa (Canada).     

On Lipschitz extension from finite subsets

We prove that for every n ∈ ? there exists a metric space (X, d _X), an n-point subset S ? X, a Banach space (Z, \({\left\| \right\|_Z}\)) and a 1-Lipschitz function f: S → Z such that the Lipschitz constant of every function F: X → Z that extends f is at least a constant multiple of \(\sqrt {\log n} \). This improves a bound of Johnson and Lindenstrauss [JL84]. We also obtain the following quantitative counterpart to a classical extension theorem of Minty [Min70]. For every α ∈ (1/2, 1] and n ∈ ? there exists a metric space (X, d _X), an n-point subset S ? X and a function f: S → ?₂ that is α-Hölder with constant 1, yet the α-Hölder constant of any F: X → ?₂ that extends f satisfies \({\left\| F \right\|_{Lip\left( \alpha \right)}} > {\left( {\log n} \right)^{\frac{{2\alpha - 1}}{{4\alpha }}}} + {\left( {\frac{{\log n}}{{\log \log n}}} \right)^{{\alpha ^2} - \frac{1}{2}}}\). We formulate a conjecture whose positive solution would strengthen Ball’s nonlinear Maurey extension theorem [Bal92], serving as a far-reaching nonlinear version of a theorem of König, Retherford and Tomczak-Jaegermann [KRTJ80]. We explain how this conjecture would imply as special cases answers to longstanding open questions of Johnson and Lindenstrauss [JL84] and Kalton [Kal04].     

Quasisymmetric embeddings, the observable diameter, and expansion properties of graphs

It is shown that the edges of any n-point vertex expander can be replaced by new edges so that the resulting graph is an edge expander, and such that any two vertices that are joined by a new edge are at distance in the original graph. This result is optimal, and is shown to have various geometric consequences. In particular, it is used to obtain an alternative perspective on the recent algorithm of Arora et al. [Proceedings of the 36th Annual ACM Symposium on the Theory of Computing, 2004, pp. 222-231.] for approximating the edge expansion of a graph, and to give a nearly optimal lower bound on the ratio between the observable diameter and the diameter of doubling metric measure spaces which are quasisymmetrically embeddable in Hilbert space.     

Spatial delocalization in para-H2 clusters

We applied the quantum path integral Monte Carlo method for the study of (para-H)N (N = 5-33) clusters at T = 2 K, exploring static and dynamic order, which originates from the effects of zero-point energy, kinetic energy, and thermal fluctuations in quantum clusters. Information on dynamic structure was inferred from the asymptotic tails of the cage correlation function calculated from the centroid Monte Carlo trajectory. The centroid cage correlation function decays to zero for large clusters (N = 15-33), manifesting the interchange of molecules between different solvation shells, with statistically diminishing back interchange. Further evidence for the floppiness of para-hydrogen clusters emerges from the Monte Carlo evolution of the centroid of a tagged molecule, which exhibits significant changes in the list of its first and second solvation shells due to the interchange of molecules between these shells.