Self-consistent quantum mechanical model for the description of excitation energy transfers in molecules at interfaces

In this paper we present a quantum mechanical model to study excitation energy transfers in molecular systems located in the vicinity of an interface. The model is based on an approximate solution of the time-dependent density functional theory equations and solvent effects are introduced in terms of the integral equation formalism version of the polarizable continuum model. A unique characteristic of this model is that environment induced polarizing effects on the interacting molecules and screening effects on their interaction are included in a coherent and self-consistent way. The model is applied to different situations of the ethylene dimer in the vicinity of an air/water interface and compared with an alternative quantum electrodynamics approach.     

Regularization and preconditioning of KKT systems arising in nonnegative least‐squares problems

A regularized Newton‐like method for solving nonnegative least‐squares problems is proposed and analysed in this paper. A preconditioner for KKT systems arising in the method is introduced and spectral properties of the preconditioned matrix are analysed. A bound on the condition number of the preconditioned matrix is provided. The bound does not depend on the interior‐point scaling matrix. Preliminary computational results confirm the effectiveness of the preconditioner and fast convergence of the iterative method established by the analysis performed in this paper. Copyright © 2008 John Wiley & Sons, Ltd.     

In vitro photodynamic inactivation of Candida spp. growth and adhesion to buccal epithelial cells

In this study, photodynamic inactivation (PDI) was used to inhibit in vitro growth and adhesion of different Candida isolates to buccal epithelial cells (BEC). Experimental conditions were optimized and 25 μM toluidine blue O (TBO) and 15 min of irradiation time by light emitting diode (LED) (energy density of 180 J/cm²) were selected due to higher reductions in cellular viability obtained after treatment. Reduction media of Log₁₀ 3.41 in viable cellular growth and media of 55% in the inhibition of adhesion to buccal epithelial cells were obtained. Two fluconazole resistant isolates were susceptible to PDI (Log₁₀ 3.54 in IB05 and Log₁₀ 1.95 in CG09) and a second session of this treatment for CG09 isolate inhibited cellular viability in 100%, without producing heat. The results permit to conclude that photodynamic inactivation under these experimental conditions would be a possible alternative approach to inhibit Candida spp. cellular growth and adhesion to buccal epithelial cells.     

Periodic solutions of competition systems with delays by an average approach

A delayed competition system of Lotka-Volterra equations, with periodic coefficients, is considered. Such a differential system admits at least a periodic positive solution if and only if the corresponding autonomous, averaged system has a positive stationary solution.     

Studies on Productivity and Characterization of Polygalacturonase from <Emphasis Type="Italic">Aspergillus giganteus</Emphasis> Submerged Culture Using Citrus Pectin and Orange Waste

Polygalacturonases are part of the group of enzymes involved in pectin degradation. The aim of this work was to investigate some of the factors affecting polygalacturonase production by an Aspergillus giganteus strain and to characterize this pectinolytic activity. Several carbon sources, both pure substances and natural substrates, were tested in standing cultures, and the best results were obtained with orange bagasse and purified citrus pectin. On citrus pectin as sole carbon source, the highest extracellular activity (9.5 U/ml and 40.6 U/mg protein) was obtained in 4.5-day-old cultures shaken at 120 rpm, pH 3.5 and 30°C, while on orange bagasse, the highest extracellular activity (48.5 U/ml and 78.3 U/mg protein) was obtained in 3.5-day-old cultures shaken at 120 rpm, pH 6.0 and 30°C. Optimal polygalacturonase activity was observed in assays conducted at pH 5.5–6.5 and 55–60°C. The activity showed good thermal stability, with half-lives of 90 and 30 min when incubated at 55 and 60°C, respectively. High stability was observed from pH 4.5 to 8.5; more than 90% of the activity remained after 24 h in this pH range.     

Active-site models for the nickel-iron hydrogenases: effects of ligands on reactivity and catalytic properties

Described are new derivatives of the type [HNiFe(SR)(2)(diphosphine)(CO)(3)](+), which feature a Ni(diphosphine) group linked to a Fe(CO)(3) group by two bridging thiolate ligands. Previous work had described [HNiFe(pdt)(dppe)(CO)(3)](+) ([1H](+)) and its activity as a catalyst for the reduction of protons (J. Am. Chem. Soc. 2010, 132, 14877). Work described in this paper focuses on the effects on properties of NiFe model complexes of the diphosphine attached to nickel as well as the dithiolate bridge, 1,3-propanedithiolate (pdt) vs 1,2-ethanedithiolate (edt). A new synthetic route to these Ni-Fe dithiolates is described, involving reaction of Ni(SR)(2)(diphosphine) with FeI(2)(CO)(4) followed by in situ reduction with cobaltocene. Evidence is presented that this route proceeds via a metastable μ-iodo derivative. Attempted isolation of such species led to the crystallization of NiFe(Me(2)pdt)(dppe)I(2), which features tetrahedral Fe(II) and square planar Ni(II) centers (H(2)Me(2)pdt = 2,2-dimethylpropanedithiol). The new tricarbonyls prepared in this work are NiFe(pdt)(dcpe)(CO)(3) (2, dcpe = 1,2-bis(dicyclohexylphosphino)ethane), NiFe(edt)(dppe)(CO)(3) (3), and NiFe(edt)(dcpe)(CO)(3) (4). Attempted preparation of a phenylthiolate-bridged complex via the FeI(2)(CO)(4) + Ni(SPh)(2)(dppe) route gave the tetrametallic species [(CO)(2)Fe(SPh)(2)Ni(CO)](2)(μ-dppe)(2). Crystallographic analysis of the edt-dcpe compund [2H]BF(4) and the edt-dppe compound [3H]BF(4) verified their close resemblance. Each features pseudo-octahedral Fe and square pyramidal Ni centers. Starting from [3H]BF(4) we prepared the PPh(3) derivative [HNiFe(edt)(dppe)(PPh(3))(CO)(2)]BF(4) ([5H]BF(4)), which was obtained as a ～2:1 mixture of unsymmetrical and symmetrical isomers. Acid-base measurements indicate that changing from Ni(dppe) (dppe = Ph(2)PCH(2)CH(2)PPh(2)) to Ni(dcpe) decreases the acidity of the cationic hydride complexes by 2.5 pK(a)(PhCN) units, from ～11 to ～13.5 (previous work showed that substitution at Fe leads to more dramatic effects). The redox potentials are more strongly affected by the change from dppe to dcpe, for example the [2](0/+) couple occurs at E(1/2) = -820 for [2](0/+) vs -574 mV (vs Fc(+/0)) for [1](0/+). Changes in the dithiolate do not affect the acidity or the reduction potentials of the hydrides. The acid-independent rate of reduction of CH(2)ClCO(2)H by [2H](+) is about 50 s(-1) (25 °C), twice that of [1H](+). The edt-dppe complex [2H](+) proved to be the most active catalyst, with an acid-independent rate of 300 s(-1).     

A Light‐Activated Olefin Metathesis Catalyst Equipped with a Chromatic Orthogonal Self‐Destruct Function

A sulfur‐chelated photolatent ruthenium olefin metathesis catalyst has been equipped with supersilyl protecting groups on the N‐heterocyclic carbene ligand. The silyl groups function as an irreversible chromatic kill switch, thus decomposing the catalyst when it is irradiated with 254 nm UV light. Therefore, different types of olefin metathesis reactions may be started by irradiation with 350 nm UV light and prevented by irradiation with shorter wavelengths. The possibility to induce and impede catalysis just by using light of different frequencies opens the pathway for stereolithographic applications and novel light‐guided chemical sequences.     

A facile C-C bond cleavage in the epoxides and its use for the synthesis of oxygenated heterocycles by a ring expansion strategy

The bicyclic epoxy alcohols when treated with DAST gave a new class of rearranged organofluorine compounds, by a ring expansion via C-C bond cleavage of the oxirane ring. The outcome of this reaction with respect to ring size and stereochemical relation between the functionalities is presented here.     

Multiple positive solutions of the stationary Keller–Segel system

We consider the stationary Keller–Segel equation

$$\begin{aligned} {\left\{ \begin{array}{ll} -\Delta v+v=\lambda e^v, \quad v>0 \quad &{} \text {in }\Omega ,\\ \partial _\nu v=0 &{}\text {on } \partial \Omega , \end{array}\right. } \end{aligned}$$

where \(\Omega \) is a ball. In the regime \(\lambda \rightarrow 0\), we study the radial bifurcations and we construct radial solutions by a gluing variational method. For any given \(n\in \mathbb {N}_0\), we build a solution having multiple layers at \(r_1,\ldots ,r_n\) by which we mean that the solutions concentrate on the spheres of radii \(r_i\) as \(\lambda \rightarrow 0\) (for all \(i=1,\ldots ,n\)). A remarkable fact is that, in opposition to previous known results, the layers of the solutions do not accumulate to the boundary of \(\Omega \) as \(\lambda \rightarrow 0\). Instead they satisfy an optimal partition problem in the limit.

     

On an asymptotic distribution of dependent random variables on a 3-dimensional lattice

We define conditions under which sums of dependent spatial data will be approximately normally distributed. A theorem on the asymptotic distribution of a sum of dependent random variables defined on a 3-dimensional lattice is presented. Examples are also presented.