Unexpected Factors Affecting the Kinetics of Guest Molecule Release from Investigation of Binary Chemical Systems Trapped in a Single Void of Mesoporous Silica Particles

In this work, we present results for loading of well-defined binary systems (cocrystal, solid solution) and untreated materials (physical mixtures) into the voids of MCM-41 mesoporous silica particles employing three different filling methods. The applied techniques belong to the group of “wet methods” (diffusion supported loading – DiSupLo ) and “solvent-free methods” (mechanical ball-mill loading – MeLo , thermal solvent free – TSF ). As probes for testing the guest1-guest2 interactions inside the MCM-41 pores we employed the benzoic acid ( BA ), perfluorobenzoic acid ( PFBA ), and 4-fluorobenzoic acid ( 4-FBA ). The guests intermolecular contacts and phase changes were monitored employing magic angle spinning (MAS) NMR Spectroscopy techniques and powder X-ray diffraction (PXRD). Since mesoporous silica materials are commonly used in drug delivery system research, special attention has been paid to factors affecting guest release kinetics. It has been proven that not only the content and composition of binary systems, but also the loading technique have a strong impact on the rate of guests release. Innovative methods of visualizing differences in release kinetics are presented.     

Fekete-Szegö problem for close-to-convex functions with respect to a certain convex function dependent on a real parameter

Given α ∈ [0, 1], let h _α (z):= z/(1 - αz), z ∈ D:= {z ∈ D: |z| < 1}. An analytic standardly normalized function f in D is called close-to-convex with respect to h _α if there exists δ ∈ (-π/2, π/2) such that Re{e^iδ zf′(z)/h _α (z)} > 0, z ∈ D. For the class ? (h _α ) of all close-to-convex functions with respect to h _α , the Fekete-Szegö problem is studied.     

How realistic is the pore size distribution calculated from adsorption isotherms if activated carbon is composed of fullerene-like fragments?

A plausible model for the structure of non-graphitizing carbon is one which consists of curved, fullerene-like fragments grouped together in a random arrangement. Although this model was proposed several years ago, there have been no attempts to calculate the properties of such a structure. Here, we determine the density, pore size distribution and adsorption properties of a model porous carbon constructed from fullerene-like elements. Using the method proposed recently by Bhattacharya and Gubbins (BG), which was tested in this study for ideal and defective carbon slits, the pore size distributions (PSDs) of the initial model and two related carbon models are calculated. The obtained PSD curves show that two structures are micro-mesoporous (with different ratio of micro/mesopores) and the third is strictly microporous. Using the grand canonical Monte Carlo (GCMC) method, adsorption isotherms of Ar (87 K) are simulated for all the structures. Finally PSD curves are calculated using the Horvath-Kawazoe, non-local density functional theory (NLDFT), Nguyen and Do, and Barrett-Joyner-Halenda (BJH) approaches, and compared with those predicted by the BG method. This is the first study in which different methods of calculation of PSDs for carbons from adsorption data can be really verified, since absolute (i.e. true) PSDs are obtained using the BG method. This is also the first study reporting the results of computer simulations of adsorption on fullerene-like carbon models.     

Electroanalytical and spectroscopic procedures for examination of interactions between double stranded DNA and intercalating drugs

A method is presented for the electroanalytical characterization of interactions of dsDNA with a drug, under conditions that both agents are dissolved in the phosphate buffer solution and both are electroactive. Normal pulse, square wave, differential pulse, and cyclic voltammetries were employed in the measurements of the drug and dsDNA oxidation signals at carbon electrodes. UV–Vis spectroscopy was used as a non-electrochemical method to support the electroanalytical data. An anticancer drug, C-1311 (5-diethylaminoethyl-amino-8-hydroxyimidazoacridinone), has been selected for the examination. Normal pulse voltammetry was particularly useful in showing that under the conditions employed neither dsDNA nor the drug were adsorbed at the electrode surface. Necessary conditions for the appearance of the well-defined dsDNA voltammetric signal (guanine peak) are: rigorous chemical and biological purity in the cell and appropriate purity of DNA. An analysis of the obtained results confirmed that there were two modes of interaction between C-1311 and dsDNA: by intercalation and electrostatically. In the presence of excess NaCl the electrostatic interactions deteriorate. The binding constants (K ₁ and K ₂, respectively) and the number (n) of nucleic base pairs (bp) and the number (m) of phosphate groups (pg) interacting with one molecule of drug have been determined. For strong interactions (intercalation) the values of the binding constant, K ₁, and the binding-site size, n, equal 3.7 × 10⁴ M⁻¹ and 2.1, respectively. For the weak electrostatic interactions the K ₂ and m parameters equal 0.28 × 10⁴ M⁻¹ and 4.7. The intercalation process is rather slow and its rate (the conditions of pseudo-first-order reaction) was estimated to equal 7 × 10⁻⁴ s⁻¹. The possibility of independent determination of both interacting agents was very useful in the study. Figure Intercalation of C-1311 into a dsDNA fragment     

Concentration on curves for nonlinear Schrödinger Equations

We consider the problem where p > 1, ε > 0 is a small parameter, and V is a uniformly positive, smooth potential. Let Γ be a closed curve, nondegenerate geodesic relative to the weighted arc length ∫_Γ V^σ, where σ = (p + 1)/(p ? 1) ? 1/2. We prove the existence of a solution u_? concentrating along the whole of Γ, exponentially small in ε at any positive distance from it, provided that ε is small and away from certain critical numbers. In particular, this establishes the validity of a conjecture raised in 3 in the two‐dimensional case. © 2006 Wiley Periodicals, Inc.     

Electronic structure of carbon trioxide and vibronic interactions involving Jahn-Teller states

The electronic structure of CO3 is characterized by equation-of-motion and coupled-cluster methods. C(2v) and D(3h) isomers are considered. Vertical excitation energies, transition dipoles, and the molecular orbital character of the excited states are presented for singlet and triplet manifolds. Ground-state equilibrium structures and frequencies are strongly affected by vibronic interactions with low-lying excited states. At D(3h) geometries, the vibronic interactions are enhanced by the Jahn-Teller character of the excited states. The curvature of the potential energy surface and the existence of the D(3h) minimum are very sensitive to the correlation treatment and the basis set. The correlation effects are stronger at D(3h), in agreement with a smaller HOMO-LUMO gap.     

Tuning intermolecular magnetic exchange interactions in the solids C(x)F(2)(x)(CNSSS)(2)(AsF(6))(2): structural, EPR, and magnetic characterization of dimeric (x = 2, 4) diradicals

A series of diradical containing salts CxF2x(CNSSS)2(**2+0(AsF6-)2 {x = 2, 1[AsF6]2; x = 3, 3[AsF6]2; x = 4, 2[AsF6]2} have been prepared. 1[AsF6]2 and 2[AsF6]2 were fully characterized by X-ray, variable-temperature magnetic susceptibility, and solid-state EPR measurements, further allowing us to extend the number of examples of the family of rare 7pi RCNSSS(*+) radical cations. 1[AsF6]2: a = 6.5314(7) A, b = 7.5658(9) A, c = 9.6048(11) A, alpha = 100.962(2) degrees , beta = 96.885(2) degrees , gamma = 107.436(2) degrees , triclinic, space group P, Z = 1, T = 173 K. 2[AsF6]2: a = 10.6398(16) A, b = 7.9680(11) A, c = 12.7468(19) A, beta = 99.758(2) degrees , monoclinic, space group P21/c, Z = 2, T = 173 K. In the solid-state, CxF2x(CNSSS)2(**2+) (x = 2, 4) formed one-dimensional polymeric chains of dications containing discrete centrosymmetric radical pairs in which radicals were linked by four centered two-electron pi*-pi* bonds [12+, d(S...S) = 3.455(1) A; 22+, d(S...S) = 3.306(2) A]. The exchange interactions in these bonds were determined to be -500 +/- 30 and -900 +/- 90 cm-1, by variable temperature magnetic susceptibility measurements, respectively, providing rare experimental data on the singlet-triplet gaps in the field of thiazyl radicals. For 2[AsF6]2, the thermally excited triplet state was unambiguously characterized by EPR techniques [/D/ = 0.0254(8) cm(-1), /E/ = 0.0013(8) cm(-1)]. These experimental data implied a weakly associated nature of the radical moieties contained in the solids 1[AsF6]2 and 2[AsF6]2. Computational analysis of the dimerization process is presented, and we show that the 2c 4 electron pi*-pi* bonds in 1[AsF6]2 and 2[AsF6]2 have ca. 50% and 40% diradical character, respectively. In contrast, 3[AsF6]2.SO2, containing diradical C3F6(CNSSS)2(**2+) with an odd number of CF2 spacers, showed magnetic behavior that was consistent with the presence of monomeric radical centers in the solid state.     

Nonexistence of small,odd breathers for a class of nonlinear wave equations

In this note, we show that for a large class of nonlinear wave equations with odd nonlinearities, any globally defined odd solution which is small in the energy space decays to 0 in the local energy norm. In particular, this result shows nonexistence of small, odd breathers for some classical nonlinear Klein Gordon equations, such as the sine-Gordon equation and \(\phi ^4\) and \(\phi ^6\) models. It also partially answers a question of Soffer and Weinstein (Invent Math 136(1): 9–74, p 19 1999) about nonexistence of breathers for the cubic NLKG in dimension one.