Concentration Dependence of Anti- and Pro-Oxidant Activity of Polyphenols as Evaluated with a Light-Emitting Fe2+-Egta-H2O2 System

Hydroxyl radical (^•OH) scavenging and the regeneration of Fe²⁺ may inhibit or enhance peroxidative damage induced by a Fenton system, respectively. Plant polyphenols reveal the afore-mentioned activities, and their cumulative net effect may determine anti- or pro-oxidant actions. We investigated the influence of 17 phenolics on ultra-weak photon emission (UPE) from a modified Fenton system (92.6 µmol/L Fe²⁺, 185.2 µmol/L EGTA (ethylene glycol-bis(β-aminoethyl-ether)-N,N,N′,N,-tetraacetic acid) and 2.6 mmol/L H₂O₂ pH = 7.4). A total of 8 compounds inhibited (antioxidant effect), and 5 enhanced (pro-oxidant effect) UPE at all studied concentrations (5 to 50 µmol/L). A total of 4 compounds altered their activity from pro- to antioxidant (or vice versa) along with increasing concentrations. A total of 3 the most active of those (ferulic acid, chlorogenic acid and cyanidin 3-O-glucoside; mean UPE enhancement by 63%, 5% and 445% at 5 µmol/L; mean UPE inhibition by 28%, 94% and 24% at 50 µmol/L, respectively) contained catechol or methoxyphenol structures that are associated with effective ^•OH scavenging and Fe²⁺ regeneration. Most likely, these structures can determine the bidirectional, concentration-dependent activity of some phenolics under stable in vitro conditions. This is because the concentrations of the studied compounds are close to those occurring in human fluids, and this phenomenon should be considered in the case of dietary supplementation with isolated phenolics.     

Subtraction Menger algebras

We give an abstract characterization of algebras of partial functions from A ⁿ to A endowed with the operations of the Menger superposition and the set-theoretic difference of functions as subsets of A ⁿ⁺¹.     

Multiplicity of periodic solutions to symmetric delay differential equations

By applying the method based on the usage of the equivariant gradient degree introduced by G?ba (1997) and the cohomological equivariant Conley index introduced by Izydorek (2001), we establish an abstract result for G-invariant strongly indefinite asymptotically linear functionals showing that the equivariant invariant ${\omega(\nabla \Phi)}$ , expressed as that difference of the G-gradient degrees at infinity and zero, contains rich numerical information indicating the existence of multiple critical points of ${\Phi}$ exhibiting various symmetric properties. The obtained results are applied to investigate an asymptotically linear delay differential equation $$x\prime = - \nabla f \big ({x \big (t - \frac{\pi}{2} \big )} \big ), \quad x \in V \qquad \quad (*)$$ (here ${f : V \rightarrow \mathbb{R}}$ is a continuously differentiable function satisfying additional assumptions) with Γ-symmetries (where Γ is a finite group) using a variational method introduced by Guo and Yu (2005). The equivariant invariant ${\omega(\nabla \Phi) = n_{1}({\bf H}_{1}) + n_{2}({\bf H}_{2}) + \cdots + n_{m}({\bf H}_{m})}$ in the case n _k ≠ 0 (for maximal twisted orbit types (H _k )) guarantees the existence of at least |n _k | different G-orbits of periodic solutions with symmetries at least (H _k). This result generalizes the result by Guo and Yu (2005) obtained in the case without symmetries. The existence of large number of nonconstant periodic solutions for (*) (classified according to their symmetric properties) is established for several groups Γ, with the exact value of ${\omega(\,\nabla \Phi)}$ evaluated.     

Calcium imaging using fluorescence lifetimes and long-wavelength probes

We describe imaging of calcium concentrations using the long-wavelength Ca²⁺ indicators, Calcium Green, Orange, and Crimson. The lifetimes of these probes were measured using the frequency-domain method and were found to increase from 50% to severalfold in response to calcium. The two-dimensional images of the calcium concentration were obtained using a new apparatus for fluorescence lifetime imaging (FLIM). We also describe procedures to correct for the position-dependent frequency response of the gain-modulated image intensifier used in the FLIM apparatus. Importantly, the FLIM method does not require the probe to display shifts in the excitation or emission spectra. Using the FLIM method, calcium imaging is possible using probes which display changes in lifetime in response to calcium. Consequently, calcium imaging is possible with excitation wavelengths ranging from 488 to as long as 620 nm, where autofluorescence and/or photochemical damage is minimal. These probes are also suitable for calcium measurements of single cells using lifetime-based flow cytometry.     

Synthesis and 1H NMR characterization of substituted 1-amino-9-imino-4-nitro-9,10-dihydr oacridines as potential antitumor agents

A convenient method for the synthesis of unsubstituted and substituted 1-amino-9-imino-4-nitro-9,10-dihydroacridines, 9 and 10 , respectively, is reported. Their ¹H nmr data are reported and discussed in order to confirm the imino tautomeric structure.     

Observation of nonlinear self-trapping in triangular photonic lattices

We experimentally study light self-trapping in triangular photonic lattices induced optically in nonlinear photorefractive crystals. We observe the formation of two-dimensional discrete and gap spatial solitons originating from the first and second bands of the linear transmission spectrum.     

On σ-commutativity in Menger algebras of n-place functions

We present an abstract characterization of various types of Menger algebras of n-place functions allowing certain permutations of variables.     

Resolution of multiexponential spectral relaxation of Yt-base by global analysis of collisionally quenched samples

We measured the wavelength-dependent intensity decays of 4,9-dihydro-4,6-dimethyl-9-oxo-1H-imidazo-1,2a-purine (Y_t-base) in propanol to determine the time-resolved emission spectra and rates of spectral relaxation. We found that resolution of the spectral relaxation times was dramatically improved by global analysis of the frequency-domain data with increasing amounts of the collisional quencher CCl₄. Collisional quenching preferentially decreases the longer-lived relaxed component of the emission, thereby increasing the fractional contribution of the incompletely relaxed portion of the emission. The data could not be explained by a single spectral relaxation time, and at least two relaxation times are needed to describe the time-dependent emission center of gravity of Y_t-base.Dedicated to Professor Stefan Paszyc on the occasion of his 70th birthday.     

Willem J. Blok 1947–2003

Dedication

Willem J. Blok 1947–2003     

Interaction between rhodanine and silver species on a nanocolloidal surface and in the solid state

This paper discusses and compares molecular interactions of rhodanine (Rd), the heterocyclic compound containing N, S, and O atoms, with two forms of silver species, i.e. Ag(I) ions and silver nanocolloidal particles. Vibrational spectroscopic and powder crystallography studies on coordination of Ag(I) ions in the solid state, supported by density functional theory, clearly indicate complexation through the nitrogen (the deprotonated imino group) and exocyclic sulfur atoms. Molecules of the complex are arranged in a one‐dimensional infinite polymeric chain structure that intertwines to give a helix motif. On the other hand, adsorption geometry of Rd on the silver surface was determined by using surface‐enhancement Raman scattering (SERS) spectroscopy. Observed differences between the SERS and the normal Raman spectra of Rd suggest that Rd adsorbs on the silver species after the rearrangement of the keto‐thione form into the enol‐thiol tautomer in acidic and neutral solutions. This leads to adsorption on this silver species through the thiolate ion. On the other hand, the alkaline pH forces first N‐deprotonation of Rd, and, in consequence, the obtained anion of the keto‐thione form interacts with the silver surface as a result of the presence of lone pairs of nitrogen and sulfur atoms, similar to the case discussed for the solid state. Copyright © 2009 John Wiley & Sons, Ltd.