Application of kinetic investigations for interpretation ofn-hexane and benzene adsorption on active carbon

Differencies between the mechanism ofn-hexane and benzene adsorption on active carbon were investigated on the ground of kinetic measurements. As it has been stated, the kinetic measurements show fundamental differencies between the mechanism of adsorption in spite of analogy existing in the state of adsorption equilibrium. Within the range investigated, only the adsorption ofn-hexane follows the model of volume filling of micropores. Existence of those differencies is also confirmed by measurements of effective diffusion coefficient values as well as changes of activation energy of the diffusion—adsorption process.

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Anwendung kinetischer Untersuchungen zur Interpretation des Adsorptionsverhaltens vonn-Hexan und Benzol an Aktivkohle

Zusammenfassung Mittels kinetischer Messungen untersuchte man die Unterschiede im Mechanismus des Adsorptionsverlaufes vonn-Hexan und Benzol an Aktivkohle. Man stellte fest, daß trotz der Analogie im Adsorptionsgleichgewichtszustand die kinetischen Messungen auf prinzipielle Unterschiede im Adsorptionsmechanismus hinweisen. Im untersuchten Bereich verläuft nur die Adsorption vonn-Hexane nach dem Modell der Mikroporenvolumenausfüllung. Die auftretenden Unterschiede wurden auch durch die Berechnungen der Werte der effektiven Diffusionskoeffizienten sowie Änderungen der Aktivierungsenergie des Diffusions-Adsorptionsprozesses bestätigt.

     

Bond energy, aromatic stabilization energy and strain in IPR fullerenes

Various models applied to DFT structures and energies of 2-D and 3-D aromatic molecules shed new light on the effects of strain and aromaticity in these systems. The cyclic pi electron delocalisation does not stabilize the fullerene C60 formation; and 5-6 and 6-6 CC bonds have near-identical bond stretch potentials.     

Estimation of isotropic nuclear magnetic shieldings in the CCSD(T) and MP2 complete basis set limit using affordable correlation calculations

A linear correlation between isotropic nuclear magnetic shielding constants for seven model molecules (CH₂O, H₂O, HF, F₂, HCN, SiH₄ and H₂S) calculated with 37 methods (34 density functionals, RHF, MP2 and CCSD(T)), with affordable pcS‐2 basis set and corresponding complete basis set results, estimated from calculations with the family of polarization‐consistent pcS‐n basis sets is reported. This dependence was also supported by inspection of profiles of deviation between CBS estimated nuclear shieldings and shieldings obtained with the significantly smaller basis sets pcS‐2 and aug‐cc‐pVTZ‐J for the selected set of 37 calculation methods. It was possible to formulate a practical approach of estimating the values of isotropic nuclear magnetic shielding constants at the CCSD(T)/CBS and MP2/CBS levels from affordable CCSD(T)/pcS‐2, MP2/pcS‐2 and DFT/CBS calculations with pcS‐n basis sets. The proposed method leads to a fairly accurate estimation of nuclear magnetic shieldings and considerable saving of computational efforts. Copyright © 2013 John Wiley & Sons, Ltd.     

Acylation of novobiocin by carboxylic acid anhydrides: preparation and characterization of semi-synthetic novenamines

The acylation of novobiocin by carboxylic acid anhydrides leading to preparation of three families of semi-synthetic acylated novenamine analogues is reported. ESI-MS was used to monitor the reaction progress and enabled the isolation of intermediate compounds that provided insights into the sequence of acylation steps during the reaction. The chemoselectivity of the reaction depends on the carboxylic acid anhydride. The potential of the acylated novenamine analogues as leads for the development of antibacterial agents is discussed.     

The measure of a translated ball in uniformly convex spaces

Let (E, ¦·¦) be a uniformly convex Banach space with the modulus of uniform convexity of power type. Let be the convolution of the distribution of a random series inE with independent one-dimensional components and an arbitrary probability measure onE. Under some assumptions about the components and the smoothness of the norm we show that there exists a constant such that |{·<t}–{·+r<t}|r ^q , whereq depends on the properties of the norm. We specify it in the case ofL spaces, >1.     

The complexity of many cells in arrangements of planes and related problems

We consider several problems involving points and planes in three dimensions. Our main results are: (i) The maximum number of faces boundingm distinct cells in an arrangement ofn planes isO(m ^2/3 n logn +n ²); we can calculatem such cells specified by a point in each, in worst-case timeO(m ^2/3 n log³ n+n ² logn). (ii) The maximum number of incidences betweenn planes andm vertices of their arrangement isO(m ^2/3 n logn+n ²), but this number is onlyO(m ^3/5– n ^4/5+2 +m+n logm), for any>0, for any collection of points no three of which are collinear. (iii) For an arbitrary collection ofm points, we can calculate the number of incidences between them andn planes by a randomized algorithm whose expected time complexity isO((m ^3/4– n ^3/4+3 +m) log² n+n logn logm) for any>0. (iv) Givenm points andn planes, we can find the plane lying immediately below each point in randomized expected timeO([m ^3/4– n ^3/4+3 +m] log² n+n logn logm) for any>0. (v) The maximum number of facets (i.e., (d–1)-dimensional faces) boundingm distinct cells in an arrangement ofn hyperplanes ind dimensions,d>3, isO(m ^2/3 n ^d/3 logn+n ^d–1). This is also an upper bound for the number of incidences betweenn hyperplanes ind dimensions andm vertices of their arrangement. The combinatorial bounds in (i) and (v) and the general bound in (ii) are almost tight.Work on this paper by the first author has been supported by Amoco Fnd. Fac. Dev. Comput. Sci. 1-6-44862 and by NSF Grant CCR-8714565. Work by the third author has been supported by Office of Naval Research Grant N00014-87-K-0129, by National Science Foundation Grant DCR-82-20085, by grants from the Digital Equipment Corporation, and the IBM Corporation, and by a research grant from the NCRD—the Israeli National Council for Research and Development. An abstract of this paper has appeared in theProceedings of the 13th International Mathematical Programming Symposium, Tokyo, 1988, p. 147.     

An Asymptotic Ratio in the Complete Binary Tree

Let T _n be the complete binary tree of height n considered as the Hasse-diagram of a poset with its root 1 _n as the maximum element. For a rooted tree T, define two functions counting the embeddings of T into T _n as follows A(n;T)=|{S T _n  : 1 _n ∈S, S≅T}|, and B(n;T)=|{S T _n :1 _n ∉S, S≅T}|. In this paper we investigate the asymptotic behavior of the ratio A(n;T)/B(n;T), and we show that lim  _n→∞[A(n;T)/B(n;T)]=2^ℓ;−1−1, for any tree T with ℓ leaves. This revised version was published online in June 2006 with corrections to the Cover Date.     

Air-dispersion measurement by second-harmonic heterodyne interferometry

Interferometers with long optical paths in air usually require knowledge and control of air dispersion. In addition, the measurements at several wavelengths and the dispersion properties of air allow errors caused by air turbulence to be compensated for. An innovative technique for air-dispersion measurement is described for long-baseline ground-based stellar interferometers. The technique combines second-harmonic interferometry and heterodyne detection to permit high-resolution measurement even for low optical powers. Experimental results show measurements of air dispersion in good agreement with the values predicted from the Edlén equation.     

Fission fragment mass yields of Th to Rf even-even nuclei

Fission properties of the actinide nuclei are deduced from theoretical analysis. We investigate potential energy surfaces and fission barriers and predict the fission fragment mass yields of actinide isotopes. The results are compared with experimental data where available. The calculations were performed in the macroscopic-microscopic approximation with the Lublin-Strasbourg Drop (LSD) for the macroscopic part, and the microscopic energy corrections were evaluated in the Yukawa-folded potential. The Fourier nuclear shape parametrization is used to describe the nuclear shape, including the non-axial degree of freedom. The fission fragment mass yields of the nuclei considered are evaluated within a 3D collective model using the Born-Oppenheimer approximation.     

Helical twisting power of antiferroelectric chiral terphenyls in different matrices

To determine the influence of chemical structure on the Helical Twisting Power (HTP), we tested four optically active dopants having a terphenyl rigid core and the same chiral centre but differing in the length of nonchiral terminal chain and the substitution of benzene rings with fluorine atoms. The compounds were added to different achiral liquid crystalline matrices: nematic and smectic C. It was found that HTP as well as its temperature variation depends on the kind of used matrices. It gives a conclusion that information about HTP obtained in one matrix cannot be uncritically transferred to another one.