Hydroxyl Radical Generation and DNA Nuclease Activity: A Mechanistic Study Based on a Surface‐Immobilized Copper Thioether Clip‐Phen Derivative

Coordination compounds of copper have been invoked as major actors in processes involving the reduction of molecular oxygen, mostly with the generation of radical species the assignment for which has, so far, not been fully addressed. In the present work, we have carried out studies in solution and on surfaces to gain insights into the nature of the radical oxygen species (ROS) generated by a copper(II) coordination compound containing a thioether clip‐phen derivative, 1,3‐bis(1,10‐phenanthrolin‐2‐yloxy)‐N‐(4‐(methylthio)benzylidene)propan‐2‐amine (2CP‐Bz‐SMe), enabling its adsorption/immobilization to gold surfaces. Whereas surface plasmon resonance (SPR) and electrochemistry of the adsorbed complex indicated the formation of a dimeric Cu^I intermediate containing molecular oxygen as a bridging ligand, scanning electrochemical microscopy (SECM) and nuclease assays pointed to the generation of a ROS species. Electron paramagnetic resonance (EPR) data reinforced such conclusions, indicating that radical production was dependent on the amount of oxygen and H₂O₂, thus pointing to a mechanism involving a Fenton‐like reaction that results in the production of OH^..     

Fractional damping enhances chaos in the nonlinear Helmholtz oscillator

Nonlinear Dynamics - The main purpose of this paper is to study both the underdamped and the overdamped dynamics of the nonlinear Helmholtz oscillator with a fractional-order damping. For that...     

Finite element techniques in plane limit problems

Summary Limit analysis of plane structures is formulated by applying a finite element linear programming technique that was previously proposed by the same author.Three different element models are considered: the constant stress compatible model, the linear stress equilibrium model, the quadratic stress equilibrium model. Some notes are devoted to the construction of the stress fields with reference to the adopted method.Some suitably chosen numerical applications are then proposed in order to compare the different approaches as far as numerical efficiency and result accuracy are concerned. The possibility of improving the linear programming procedure is also discussed, and in particular a method is proposed to find out an initial feasible vector on the basis of mechanical considerations, in order to overcome the necessity of the so-called M-phase of the simplex method.Numerical results are given together with the comments.

---

Sommario Si formula il problema dell'analisi limite di strutture piane secondo un metodo degli elementi finiti già proposto dall'autore.Nel presente lavoro vengono considerati tre diversi modelli di elementi e precisamente: il modello congruente a sforzo costante e quelli equilibrati a campi di sforzo lineare e quadratico. La costruzione dei tre modelli viene presentata in dettaglio nell'ambito del metodo adottato.Vengono quindi presentati alcuni esempi di applicazione opportunamente scelti, con lo scopo di confrontare l'efficienza numerica e l'accuratezza di risultati ottenuti con l'impiego dei tre modelli. Si discute inoltre la possibilità di migliorare l'efficacia dell'algoritmo matematico ed in particolare si suggerisce un metodo che, individuando una soluzione ammissibile di partenza sulla scorta di considerazioni meccaniche, permette di evitare la cosiddetta fase M della programmazione lineare.I commenti sono accompagnati dai risultati numerici.

---

---

Research supported by the C.N.R. (Italian National Research Council).     

Poly(ethylene glycol)-b-poly(1,3-trimethylene carbonate) Amphiphilic Copolymers for Long-Acting Injectables: Synthesis,Non-Acylating Performance and In Vivo Degradation

This article presents the evaluation of diblock and triblock poly(ethylene glycol)-b-poly(1,3-trimethylene carbonate) amphiphilic copolymers (PEG-PTMCs) as excipients for the formulation of long-acting injectables (LAIs). Copolymers were successfully synthesised through bulk ring-opening polymerisation. The concomitant formation of PTMC homopolymer could not be avoided irrespective of the catalyst amount, but the by-product could easily be removed by gel chromatography. Pure PEG-PTMCs undergo faster erosion in vivo than their corresponding homopolymer. Furthermore, these copolymers show outstanding stability compared to their polyester analogues when formulated with amine-containing reactive drugs, which makes them particularly suitable as LAIs for the sustained release of drugs susceptible to acylation.     

Ueber F?ulnissalkaloide

Ohne Zusammenfassung     

Solid‐state 13C and 129Xe NMR study of poly(vinyl alcohol) and poly(vinyl alcohol)/lactosilated chitosan gels

Dry and hydrated poly(vinyl alcohol) (PVA) gels with 55% (a‐PVA) and 61% (s‐PVA) syndiotacticity and related PVA/lactyl chitosan (LC) blends have been investigated with ¹²⁹Xe and cross‐polarization/magic‐angle‐spinning ¹³C NMR techniques. Although the dry gels exhibit two broad ¹²⁹Xe resonances in the slow‐to‐intermediate exchange limit, both hydrated gels show three resonances. The corresponding dry blends exhibit two signals, the chemical shifts and line widths of which change with respect to those of pure PVA, whereas one (a‐PVA/LC) or two (s‐PVA/LC) signals appear in the spectra of the hydrated blends. A comparative analysis of the data demonstrates that LC rearranges the domains of the polymeric matrix in both the dry and hydrated blends according to the syndiotacticity of the PVA chains. Information on the molecular motions of the amorphous and swollen polymeric domains in the kilohertz range has been obtained from an analysis of the spin‐lattice relaxation times. These data indicate that the dynamics and arrangement of the PVA chains in the gels are strongly affected by their tacticity and the addition of the copolymer LC. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3123–3131, 2003     

Optical hole burning and matrix effects in a phthalocyanine complex of ruthenium(II)

A doubling of the origin is observed in the low-temperature electronic absorption spectrum of the complex carbonyl(pyridine)-phthalocyaninatoruthenium(II) in glassy matrices. The effect is studied by optical hole burning and results suggest a non-degenerate singlet ground state of near C_2v symmetry to be invoked.