No abstract

Novel amine- or ammonium-terminated carbosilane dendrimers of type nG-[Si{OCH2(C6H3)-3,5-(OCH2CH2NMe2)2}]x, nG-[Si{O(CH2)2N(Me)(CH2)2NMe2}]x and nG-[Si{(CH2)3NH2}]x or nG-[Si{OCH2(C6H3)-3,5-(OCH2CH2NMe3 +I-)2}]x, nG-[Si{O(CH2)2N(Me)(CH2)2NMe3 +I-}]x, and nG-[Si{(CH2)3NH3 +Cl-}]x have been synthesized and characterized up to the third generation by two strategies: 1) alcoholysis of Si--Cl bonds with amino alcohols and subsequent quaternization with MeI, and 2) hydrosilylation of allylamine with Si--H bonds of the dendritic systems and subsequent quaternization with HCl. Quaternized carbosilane dendrimers are soluble in water, although degradation is apparent due to hydrolysis of Si--O bonds. However, dendrimers containing Si--C bonds are water-stable. The biocompatibility of the second-generation dendrimers in primary cell cultures of peripheral blood mononuclear cells (PBMCs) and erythrocytes have been analyzed, and they show good toxicity profiles over extended periods. In addition, we describe a study on the interactions between the different carbosilane dendrimers and DNA oligodeoxynucleotides (ODNs) and plasmids along with a comparative analysis of their toxicity. They can form complexes with DNA ODNs and plasmids at biocompatible doses via electrostatic interaction. Also a preliminary transfection assay has been accomplished. These results demonstrate that the new ammonium-terminated carbosilane dendrimers are good base molecules to be considered for biomedical applications.

The aim of this work was to design strategies to improve the performance of solid-state lasers and amplifiers based on perylenediimide (PDI) derivatives as active materials. So, the effect of different types of modifications of the chemical structure of PDIs in their spectral, electrochemical, and laser properties in both solution and PDI-doped polystyrene films at various concentrations has been investigated. In particular, we focused on controlling the wavelength of emission in order to tune the laser wavelength as well as in increasing the amount of PDI in the films in order to decrease the laser thresholds, while keeping a good photostability. Three types of modifications of the chemical structure were investigated: (a) symmetrical substitution at the imide nitrogen positions (PDI 1); (b) substitution at the bay positions in the PDI core (PDI 4); and (c) modification in the dicarboximide group (PDI 5). All three derivatives were soluble and showed good n-type acceptor ability. Routes b and c led to red shifts in the absorption and photoluminescence (PL) emission, although the PL quantum yield decreased considerably. Amplified spontaneous emission (ASE) was observed in films doped with PDI 1 (λ ) 579 nm) and PDI 4 (λ ) 599 nm). The best performance, with an ASE threshold of 15 kW/cm 2 and a photostability halflife of 31 × 10 3 pump pulses, was obtained for films doped with 0.75 wt % of PDI 1 (route 1). PDI 1-based materials are among the most photostable reported in the literature and show very-reasonable thresholds. Moreover, these materials are particularly interesting in the field of data communications based on polymer optical fibers because they emit at wavelengths close to 570 nm, which constitutes the second low-loss transmission window in poly(methyl methacrylate).

No abstract

Herein, the synthesis and self-assembling features of N-heterotriangulenes 1-3 decorated in their periphery with 3,4,5-trialkoxy-N-(alkoxy)benzamide moieties that enable kinetic control of the supramolecular polymerization process are described. The selection of an appropriate solvent results in a tunable energy landscape in which the relative energy of the different monomeric or aggregated species can be regulated. Thus, in a methylcyclohexane/toluene (MCH/Tol) mixture, intramolecular hydrogen-bonding interactions in the peripheral side units favor the formation of metastable inactivated monomers that evolve with time at precise conditions of concentration and temperature. A pathway complexity in the supramolecular polymerization of 1-3 cannot be determined in MCH/Tol mixtures but, importantly, this situation changes by using CCl . In this solvent, the off-pathway product is a face-to-face H-type aggregate and the on-pathway product is the slipped face-to-face J-type aggregate. The autocatalytic transformation of the metastable monomeric units, as well as the two competing off- and on-pathway aggregates allow the realization of seeded and living supramolecular polymerizations. Interestingly, the presence of chiral, branched side chains in chiral (S)-2 noticeably retards the kinetics of the investigated transformations. This work brings to light the relevance of controlling the pathway complexity in self-assembling units and opens new avenues for the investigation of complex and functional supramolecular structures.

The formation of helical structures through the supramolecular polymerization of a variety of self‐assembling units is reviewed. These scaffolds are usually obtained by efficient transfer or amplification of chirality phenomena, in which the starting self‐assembling molecules possess different elements of asymmetry, such as point or axial chirality. Relevant examples of helical supramolecular structures investigated under thermodynamic control are reviewed, and the helical outcome of remarkable examples of chiral entities obtained through kinetic control are also highlighted. Finally, selected examples of flexible macroscopic chirality and catalysis are described to illustrate the applicability of helical aggregates.

We describe the synthesis and characterization of a novel poly(fluorene-alt-phenylene) substituted with perylenediimide (PDI) moieties as pendant groups. Cyclic voltammetry experiments show the amphoteric nature of the material, which combines the good electron donor ability of the polymeric chain with the acceptor properties of the pendant PDI moieties. Absorption spectroscopy suggests the presence of PDI aggregates, whereas the emission spectra show a strong emission quenching of both the polymeric backbone and the PDI units. Further investigation on the energy and/or electron-transfer processes involved is carried out by temperature-dependent excitation spectra and photoluminescence lifetimes. These studies show the presence of electron transfer not only from the electron donor polymeric chain to the pendant PDI units but also, and more remarkably, to PDI aggregates both in solution and in solid state, as is further confirmed by photoinduced absorption spectroscopy.

Recently, antimicrobial peptides (AMPs), also called host defence peptides (HDPs), are attracting great interest, as they are a highly viable alternative in the search of new approaches to the resistance presented by bacteria against antibiotics in infectious diseases. However, due to their nature, they present a series of disadvantages such as low bioavailability, easy degradability by proteases, or low solubility, among others, which limits their use as antimicrobial agents. For all these reasons, the use of vehicles for the delivery of AMPs, such as polymers, nanoparticles, micelles, carbon nanotubes, dendrimers, and other types of systems, allows the use of AMPs as a real alternative to treatment with antibiotics.