Adsorption of chlorobenzene vapor on V<Subscript>2</Subscript>O<Subscript>5</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst under dynamic conditions

Adsorption dynamics of chlorobenzene vapors on a 5% V₂O₅/Al₂O₃ catalyst has been investigated using the frontal chromatography technique. The uptakes of chlorobenzene have been measured as a function of vapor concentration and adsorption equilibrium has been found to follow formally the Langmuir isotherm. The breakthrough time proved to be a linear function of the column length as expected. Breakthrough profiles have been reported for different experimental conditions and quantitatively fitted by a reduced lumped diffusion model. This model provides an analytical solution that facilitates engineering calculations. Model parameters show complex behavior as functions of stream characteristics and depend on column length. When empirical expressions relating model mass transfer coefficients with influencing variables are found the model demonstrates good accuracy in predicting column performance.     

Synthesis,characterization and assessment of the cytotoxic activity of Cu(II), Fe(III) and Mn(III) complexes of camphoric acid‐derived salen ligands

Novel Cu(II), Fe(III) and Mn(III) salen‐type metal complexes from (1R,3S)‐N,N′‐bis[salicylidene]‐1,3‐diamino‐1,2,2‐trimethylcyclopentane were synthesized and screened for their in vitro cytotoxic activity against three human cancer cell lines: melanoma, colorectal and breast. In vitro experiments carried out with the three metal complexes show that the copper complex exhibits the highest cytotoxic activity towards all cell lines studied, presenting IC₅₀ values of 3.32–6.71 μM. A significant improvement in the anti‐proliferative effect, by 20‐fold, is observed with this complex when compared with conventional chemotherapy. The relationship between structure, redox characteristics and biological activity in human cancer cell lines was evaluated for the most efficient Cu(II) complex and associated with theoretical calculations. Copyright © 2015 John Wiley & Sons, Ltd.     

Femtosecond pump-probe measurements of solvation by hydrogen-bonding interactions.

An additional ultrafast blue shift in the transient absorption spectra of hydrogen-bonding complexes of a strong photoacid, 8-hydroxypyrene 1,3,6-trisdimethylsulfonamide (HPTA), over the solvation response of the uncomplexed HPTA and also over that of the methoxy derivative of the photoacid (MPTA) in the presence of the hydrogen-bonding base was observed on optical excitation of the photoacid. The additional 55 +/- 10 fs solvation response was found to be about 35 % and 19% of the total C(t) of HPTA in dichloromethane (DCM) when it was hydrogen-bonded to dimethylsulfoxide (DMSO) and dioxane, respectively, and about 29% of the total C(t) of HPTA in dichloroethane (DCE) when it was hydrogen-bonded to DMSO. We have assigned this additional dynamic spectral shift to a transient change in the hydrogen bond (O-H...O) that links HPTA to the complexing base, after the electronic excitation of the photoacid.     

Scaling behavior of surface irregularity in the molecular domain: From adsorption studies to fractal catalysts

For an unexpected variety of solids, the surface topography from a few up to as many as a thousand angstroms is very well described by fractal dimension,D. This follows from measurements of the number of molecules in surface monolayers, as function of adsorbate or adsorbent particle size. As an illustration, we present a first case, amorphous silica gel, whereD has been measured independently by each of the two methods. (The agreement, 3.02±0.06 and 3.04±0.05, is excellent, and the result is modeled by a heavy generalized Menger sponge.) The examples as a whole divide into amorphous and crystalline materials, but presumably all of them are to be modeled as random fractal surfaces. The observedD values exhaust the whole range between 2 and 3, suggesting that there are a number of different mechanisms by which such statistically self-similar surfaces form. We show that fractal surface dimension entails interfacial power laws much beyond what is the source of theseD values. Examples are reactive scattering events when neutrons of variable flux pass the surface (this is of interest for locating fractal substrates that may support adlayer phase transitions); the rate of diffusion-controlled chemical reactions at fractal surfaces; and the fractal implementation of the traditional idea that the active sites of a catalyst are edge and apex sites on the surface.     

Lithium insertion into titanium dioxide (anatase) electrodes: microstructure and electrolyte effects

Insertion characteristics of anatase electrodes were studied on single-crystal and polycrystalline electrodes of different microstructures. The lithium incorporation from propylene carbonate solution containing LiClO₄ and Li(CF₃SO₂)₂N was studied by means of cyclic voltammetry (CV), the quartz crystal microbalance (QCM) and the galvanostatic intermittent titration technique (GITT). The electrode microstructure affects both the accessible coefficient x and the reversibility of the process. The highest insertion activity was observed for electrodes composed of crystals with characteristic dimensions of ∼10^–8 m. The insertion properties deteriorate for higher as well as for smaller crystal sizes. Enhanced insertion was observed in Li(CF₃SO₂)₂N-containing solutions. Lithium insertion is satisfactorily reversible for mesoscopic electrodes; the reversibility in the case of compact polycrystalline and single-crystal electrodes is poor. The reversibility of the insertion improves with increasing electrolyte concentration. The lithium diffusion coefficient decreases with increasing x and ranges between 10^–15 and 10^–18 cm² s^–1. Electronic Publication     

The Kepler problem spinor regularization and quantization on the manifolds S2

Summary In a previous research we have shown that the KS-transformation, developed by Kustaanheimo and Stiefel for the regularization of the Kepler problem, may be interpreted as the correspondence which associates to each null 4-vector of the space of Minkowski a one-index spinor, defined up to a phase factor, and we have obtained a new form of the KS-transformation. In the present research we show that this formulation allows a straight derivation of the Hopf fibering of the sphere S³ (characterized by unit spinors) having the base space given by the section (sphere S²) of the light cone, and we show that the KS-transformation allows the quantization of the symplectic manifold S² in the sense of Souriau. The sphere S³ turns out to be a contact quantized manifold. The bilinear relation characteristic of the KS-theory and the column vectors of the KS-matrix are intimately related to the contact structure.

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Sommario In un precedente lavoro si è mostrato che la trasformazione KS, introdotta da Kustaanheimo e Stiefel per regolarizzare il problema di Keplero, è riconducibile alla ben nota corrispondenza fra vettori del cono isotropo dello spazio di Minkowski e spinori semplici, definiti a meno della fase, e si è pervenuti ad una nuova formulazione della KS. Nel presente lavoro si mostra come da tale formulazione scaturisca in modo naturale la fibrazione di Hopf della sfera S³ (caratterizzata dagli spinori unitari) avente quale base una sezione (sfera S²) del cono isotropo e si mette in luce come la trasformazione KS consenta di effettuare la quantizzazione della varietà simplettica S² nel senso di Souriau e di ottenere la sfera S³ quale varietà quantica di contatto. La relazione bilineare caratteristica della teoria KS ed i vettori colonna della matrice KS risultano intimamente legati alla struttura di contatto.

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Presented at the VI Congresso Nazionale dell'Associazione Italiana di Meccanica Teorica ed Applicata (AIMETA), Genova, October 1982. Work performed under the auspices of G.N.F.M. of the C.N.R. (Consiglio Nazionale delle Ricerche).     

Analytic results for asymmetric Random Walk with exponential transition probabilities

We present here exact analytic results for a random walk on a one-dimensional lattice with asymmetric, exponentially distributed jump probabilities. We derive the generating functions of such a walk for a perfect lattice and for a lattice with absorbing boundaries. We obtain solutions for some interesting moment properties, such as mean first passage time, drift velocity, dispersion, and branching ratio for absorption. The symmetric exponential walk is solved as a special case. The scaling of the mean first passage time with the size of the system for the exponentially distributed walk is determined by the symmetry and is independent of the range.Supported by the National Science Foundation and the Department of Energy.NSF Energy Related Postdoctoral Fellow.     

Regular groups on generalized quadrangles and nonabelian difference sets with multiplier -1

This is a first approach to the study of regular generalized quadrangles (i.e. generalized quadrangles with an automorphism group sharply 1-transitive on points). In this paper we point out how the problem is connected to the theory of difference sets with multiplier-1. First, some of the results in [3] on difference sets with multiplier-1 are extended to the nonabelian case; then, these new results on difference sets are used to prove nonexistence theorems for regular GQs of even order s=t.Dedicated to Otto Wagner on the occasion of his 60th birthday