Synthesis and structure of cyclopropano-annelated homosesquinorbornene derivatives containing pyramidalized double bonds: evidence for the sterical effect of a cyclopropyl group on the degree of C=C double-bond pyramidalization

[reaction: see text] endo- and exo-2,3,4,7-tetrahydro-1H-1,4-methanobenzocycloheptene-7-carboxylic acid ethyl esters have been synthesized, and their Diels-Alder cycloaddition reactions with maleic anhydride, dimethyl acetylenedicarboxylate and singlet oxygen have been investigated. The X-ray analysis of four adducts indicated the pyramidalization of the central double bond. Density functional theory calculations on the isolated products and model compounds showed excellent agreement between the experimental and theoretical determined butterfly angles. Furthermore, it has been shown that a cyclopropyl group fused to [2.2.2] system decreases significantly the degree of the pyramidalization which is attributed to the steric interactions between the cyclopropyl group and ethano bridge of the norbornene systems. Due to the instability of the bicyclic endoperoxides, their X-ray analysis could not be carried out. DFT calculations on model compounds showed increased bending in the case of the product obtained by the addition of singlet oxygen to endo-2,3,4,7-tetrahydro-1H-1,4-methanobenzocycloheptene-7-carboxylic acid ethyl ester.     

Recognition-induced transformation of microspheres into vesicles: morphology and size control

Polystyrene functionalized with diamidopyridine (DAP) recognition units self-assembles in nonpolar media to form thermally reversible micrometer-scale spherical aggregates. The size and the thermal stability of these microspheres can be controlled by the molecular weight of the polymer. The addition of thymine-functionalized polymer to these self-assembled microspheres converted them into vesicular aggregates with a controlled size. The morphology change was reversible: the addition of DAP-functionalized polymer converted the vesicles back to microspheres.     

A-Statistical extension of the Korovkin type approximation theorem

In this paper, using the concept ofA-statistical convergence which is a regular (non-matrix) summability method, we obtain a general Korovkin type approximation theorem which concerns the problem of approximating a functionf by means of a sequenceL _n f of positive linear operators.     

Partial Geometric Difference Families

We introduce the notion of a partial geometric difference family as a variation on the classical difference family and a generalization of partial geometric difference sets. We study the relationship between partial geometric difference families and both partial geometric designs and difference families, and show that partial geometric difference families give rise to partial geometric designs. We construct several infinite families of partial geometric difference families using Galois rings and the cyclotomy of Galois fields. From these partial geometric difference families, we generate a list of infinite families of partial geometric designs and directed strongly regular graphs.     

q-Shock soliton evolution

By generating function based on Jackson’s q-exponential function and the standard exponential function, we introduce a new q-analogue of Hermite and Kampe-de Feriet polynomials. In contrast to q-Hermite polynomials with triple recurrence relations similar to [1], our polynomials satisfy multiple term recurrence relations, which are derived by the q-logarithmic function. It allows us to introduce the q-Heat equation with standard time evolution and the q-deformed space derivative. We find solution of this equation in terms of q-Kampe-de Feriet polynomials with arbitrary number of moving zeros, and solved the initial value problem in operator form. By q-analog of the Cole–Hopf transformation we obtain a new q-deformed Burgers type nonlinear equation with cubic nonlinearity. Regular everywhere, single and multiple q-shock soliton solutions and their time evolution are studied. A novel, self-similarity property of the q-shock solitons is found. Their evolution shows regular character free of any singularities. The results are extended to the linear time dependent q-Schrödinger equation and its nonlinear q-Madelung fluid type representation.     

Direct electrochemistry of uric acid at chemically assembled carboxylated single-walled carbon nanotubes netlike electrode

Carboxylated single-walled carbon nanotubes (SWCNT) chemically assembled on gold substrate was employed as netlike electrode to investigate the charge-transfer process and electrode process kinetics using uric acid as an example. The electrochemical behavior of uric acid in carboxylated SWCNT system was investigated using cyclic voltammetry, chronoamperometry, and single potential time-based techniques. The properties of raw SWCNT electrode were also studied for comparison purpose. Uric acid has better electrochemical behavior whereas ascorbic acid has no effective reaction on the carboxylated SWCNT electrode. Cyclic voltammograms indicate that the assembled carboxylated SWCNT increases more active sites on electrode surface and slows down the electron transfer between the gold electrode and uric acid in solution. The charge-transfer coefficient (alpha) for uric acid and the rate constant (k) for the catalytic reaction were calculated as 0.52 and 0.43 s(-1), respectively. The diffusion coefficient of 0.5 mM uric acid was 7.5 x 10(-6) cm2 x s(-1). The results indicate that electrode process in the carboxylated SWCNT electrode system is governed by the surface adsorption-controlled electrochemical process.     

Study on the stability of supercritical fluid extracted rosemary (<Emphasis Type="Italic">Rosmarinus offcinalis</Emphasis> L.) essential oil

The aim of this study was to examine the influence of storage conditions and duration on composition and antioxidant activity of supercritical fluid (SCF) extracted essential oil of rosemary (Rosmarinus officinalis L.). Supercritical extraction was carried out sequentially by using SCF carbondioxide in the first two steps and with 5% ethanol as entrainer in the third step. The compositions of the extracts were determined by gas chromatography/mass spectrometry. The total phenolics were analyzed using Folin-Ciocalteau assay. Antioxidant activities of the extracts were tested by β-carotene-linoleic acid bleaching method.