Mesoporous Silica Nanoparticles Decorated with Carbosilane Dendrons as New Non‐viral Oligonucleotide Delivery Carriers

A novel nanosystem based on mesoporous silica nanoparticles covered with carbosilane dendrons grafted on the external surface of the nanoparticles is reported. This system is able to transport single‐stranded oligonucleotide into cells, avoiding an electrostatic repulsion between the cell membrane and the negatively charged nucleic acids thanks to the cationic charge provided by the dendron coating under physiological conditions. Moreover, the presence of the highly ordered pore network inside the silica matrix would make possible to allocate other therapeutic agents within the mesopores with the aim of achieving a double delivery. First, carbosilane dendrons of second and third generation possessing ammonium or tertiary amine groups as peripheral functional groups were prepared. Hence, different strategies were tested in order to obtain their suitable grafting on the outer surface of the nanoparticles. As nucleic acid model, a single‐stranded DNA oligonucleotide tagged with a fluorescent Cy3 moiety was used to evaluate the DNA adsorption capacity. The hybrid material functionalised with the third generation of a neutral dendron showed excellent DNA binding properties. Finally, the cytotoxicity as well as the capability to deliver DNA into cells, was tested in vitro by using a human osteoblast‐like cell line, achieving good levels of internalisation of the vector DNA/carbosilane dendron‐functionalised material without affecting the cellular viability.     

Micelle‐Triggered β‐Hairpin to α‐Helix Transition in a 14‐Residue Peptide from a Choline‐Binding Repeat of the Pneumococcal Autolysin LytA

Choline‐binding modules (CBMs) have a ββ‐solenoid structure composed of choline‐binding repeats (CBR), which consist of a β‐hairpin followed by a short linker. To find minimal peptides that are able to maintain the CBR native structure and to evaluate their remaining choline‐binding ability, we have analysed the third β‐hairpin of the CBM from the pneumococcal LytA autolysin. Circular dichroism and NMR data reveal that this peptide forms a highly stable native‐like β‐hairpin both in aqueous solution and in the presence of trifluoroethanol, but, strikingly, the peptide structure is a stable amphipathic α‐helix in both zwitterionic (dodecylphosphocholine) and anionic (sodium dodecylsulfate) detergent micelles, as well as in small unilamellar vesicles. This β‐hairpin to α‐helix conversion is reversible. Given that the β‐hairpin and α‐helix differ greatly in the distribution of hydrophobic and hydrophilic side chains, we propose that the amphipathicity is a requirement for a peptide structure to interact and to be stable in micelles or lipid vesicles. To our knowledge, this “chameleonic” behaviour is the only described case of a micelle‐induced structural transition between two ordered peptide structures.     

Adding a Structural Context to the Deprotometalation and Trans‐Metal Trapping Chemistry of Phenyl‐Substituted Benzotriazole

Organometallic bases are becoming increasingly complex, because mixing components can lead to bases superior to single‐component bases. To better understand this superiority, it is useful to study metalated intermediate structures prior to quenching. This study is on 1‐phenyl‐1H‐benzotriazole, which was previously deprotonated by an in situ ZnCl₂ ? TMEDA/LiTMP (TMEDA=N,N,N′,N′‐tetramethylethylenediamine; TMP=2,2,6,6‐tetramethylpiperidide) mixture and then iodinated. Herein, reaction with LiTMP exposes the deficiency of the single‐component base as the crystalline product obtained was [{4‐R‐1‐(2‐lithiophenyl)‐1H‐benzotriazole ? 3THF}₂], [R=2‐C₆H₄(Ph)NLi], in which ring opening of benzotriazole and N₂ extrusion had occurred. Supporting lithiation by adding iBu₂Al(TMP) induces trans‐metal trapping, in which C?Li bonds transform into C?Al bonds to stabilise the metalated intermediate. X‐ray diffraction studies revealed homodimeric [(4‐R′‐1‐phenyl‐1H‐benzotriazole)₂], [R′=(iBu)₂Al(μ‐TMP)Li], and its heterodimeric isomer [(4‐R′‐1‐phenyl‐1H‐benzotriazole){2‐R′‐1‐phenyl‐1H‐benzotriazole}], whose structure and slow conformational dynamics were probed by solution NMR spectroscopy.     

Relative energy of organic compounds IV. Radicals,carbocations, and carbanions

The structure-dependent energies of organic radicals, cations, and anions are deduced from their calculated relative enthalpies and are compared to the relative enthalpies of their parent compounds. The use of relative enthalpies to express the relative energies of organic radicals, cations, and anions proved to be as fruitful as in the case of their parent organic compounds. The same energy-determining structural factors may have stronger, weaker, or even opposite effects in the radicals, cations, or anions than those in their parent molecules.     

O the volume growth of the hyperbolic regular $$\varvec{}$$-simplex

In this paper we give lower and upper bounds for the volume growth of a regular hyperbolic simplex, namely for the ratio of the n-dimensional volume of a regular simplex and the \((n-1)\)-dimensional volume of its facets. In addition to the methods of U. Haagerup and M. Munkholm we use a third volume form based on the hyperbolic orthogonal coordinates of a body. In the case of the ideal, regular simplex our upper bound gives the best known upper bound. On the other hand, also in the ideal case our general lower bound, improved the best known one for \(n=3\).     

Nonnormal Effects in the Taylor–Couette Problem

This work is devoted to the study of transient growth of perturbations in the Taylor–Couette problem due to linear nonnormal mechanisms. The study is carried out for a particular small gap case and is mostly focused on the linearly stable regime of counter-rotation. The exploration covers a wide range of inner and outer angular speeds as well as axial and azimuthal modes. Significant transient growth is found in the regime of stable counter-rotation. The numerical results are in agreement with former analyses based on energy methods and other independent numerical studies. The optimal energy transient growth factor appears to be consistent with experimental observations. This study might shed some light on the subcritical transition to turbulence which is found experimentally in Taylor–Couette flow when the cylinders rotate in opposite directions. Received 13 February 2001 and accepted 29 March 2002 Published online: 2 October 2002 RID="*" ID="*" This work was supported by the UK EPSRC under Grant GR/M30890. The author thanks Nick Trefethen for fruitful discussions. RID="*" ID="*" Present address: Departament de Fisica Aplicada, Univ. Politecnica de Catalunya, 08034 Barcelona, Spain (alvar@fa.upc.es) Communicated by H.J.S. Fernando     

Numerical approximation of a viscoelastic frictional contact problemApproximation numérique d'un problème viscoélastique de contact avec frottement

We consider a fully discrete scheme for a quasistatic frictional contact problem between a viscoelastic body and an obstacle. The contact is bilateral, the friction is modeled with Tresca's law and the behavior of the material is described with a viscoelastic constitutive law with long memory. We state an existence and uniqueness result for the discrete solution, followed by error estimate results. Then, we present numerical simulations in the study of a two-dimensional test example. To cite this article: Á. Rodríguez-Arós et al., C. R. Mecanique 334 (2006).     

Electromembrane extraction (EME) and HPLC determination of non-steroidal anti-inflammatory drugs (NSAIDs) in wastewater samples

In this paper, an electromembrane extraction (EME) combined with a HPLC procedure using diode array (DAD) and fluorescence detection (FLD) has been developed for the determination of six widely used non-steroidal anti-inflammatory drugs (NSAIDs): salicylic acid (SAC), ketorolac (KTR), ketoprofen (KTP), naproxen (NAX), diclofenac (DIC) and ibuprofen (IBU). The drugs were extracted from basic aqueous sample solutions, through a supported liquid membrane (SLM) consisting of 1-octanol impregnated in the walls of a S6/2 Accurel^® polypropylene hollow fiber, and into a basic aqueous acceptor solution resent inside the lumen of the hollow fiber with a potential difference of 10 V applied over the SLM. Extractions that were carried out in 10 min using a potential of 10 V from pH 12 NaOH aqueous solutions shown concentration enrichments factors of 28-49 in a pH 12 NaOH aqueous acceptor solution. The proposed method was successfully applied to urban wastewaters. Excellent selectivity was demonstrated as no interfering peaks were detected. The procedure allows very low detection and quantitation limits of 0.0009-9.0 and 0.003-11.1 μg L⁻¹, respectively.