Synthesis of Bifunctional Allylic Compounds by Using Cyclopropenes as Functionalized Allyl Equivalents

The synthesis of uncommon bifunctional allylic derivatives bearing a silane and an alcohol within the same allylic framework is reported. This method relies on the coupling of hydrosilanes with substituted and functionalized cyclopropenes, which deliver the allyl fragment. Rhodium(II) catalysts provide regioselective access to vinyl carbene intermediates, which easily undergo Si?H bond insertions. The transformation occurs with complete atom economy and shows a remarkably broad scope, including a intramolecular version for the synthesis of cyclic O?Si‐linked compounds as well as the synthesis of the corresponding allyl amines.     

Convergence analysis of sectional methods for solving breakage population balance equations-II: the cell average technique

This work presents the convergence of the cell average technique (Kumar et al. in Powder Technol 179:205–228, 2007) for solving breakage population balance equation. Similarly to our paper Kumar and Warnecke (Numerische Math, 2008) of this series, we study convergence on four different types of meshes. A second order convergence is proved for uniform, locally uniform and non-uniform smooth meshes. Finally the scheme is analyzed on random mesh and it is found that the scheme is only first order accurate. Nevertheless we obtain for locally uniform as well as for random mesh one order higher accuracy than the fixed pivot technique discussed by the authors in the first paper. All mathematical observations of convergence analysis are also validated numerically and numerical results are compared with the results of the first part.     

Behaviour of wetting films of sodium hyaluronate saline solutions

The behaviour of wetting films of sodium hyaluronate (NaHA) saline solutions, at physiological conditions, is investigated using interferometry. Concentrations in the range of dilute and semi-dilute regimes were chosen to assess the role of bulk molecular interactions on the surface forces. The transition from dilute to semi-dilute solutions is known to occur at c*=0.59 mg mL(-1). Dilute solutions form stable films whose behaviour is explained by van der Waals interactions. For semi-dilute solutions, the disjoining pressure vs film thickness isotherms show branches attributed to stepwise thinning or film stratification, which is interpreted in terms of a network as predicted by the theory of semi-dilute polyelectrolyte solutions. The distance between branches is 16 nm for the NaHA concentration of 2 mg mL(-1) and 12 nm for the concentration of 3.5 mg mL(-1), in agreement with the calculated correlation lengths of the polymeric network. Since no experimental evidence exists for the presence of a stable network in the bulk, this tendency for self-association should be the result of the liquid confinement. To our knowledge, the existence of oscillatory disjoining pressure isotherms in the presence of excess salt was never observed for other polyelectrolyte solutions.     

Solid-supported cross metathesis and the role of the homodimerization of the non-immobilized olefin

We have prepared immobilized olefins as models for the cross metathesis using different olefin partners in the presence of second generation Grubbs and Hoveyda-Grubbs precatalysts. We have demonstrated that solid-phase cross metathesis is strongly dependent on the degree of homodimerization of the non-immobilized olefin and the reactivity of such a homodimer. As in the homogeneous phase, the Hoveyda-Grubbs precatalyst was better for immobilized alpha,beta-unsaturated carbonyl compounds.     

Fast response in TN liquid-crystal cells: effect of functionalised carbon nanotubes

The optical response time of a nematic liquid crystal (NLC) decreases due to incorporation of carbon nanotubes (CNTs) in the liquid-crystal host. Such reduction is believed to be due to an increase in the elastic constant of the nanotube-doped LC system. In this paper, we present the effect on optical response due to doping an NLC with octadecylamine functionalised single-walled carbon nanotubes (ODA-SWCNT) in a twisted alignment mode. The electro-optic switching amplitude of ODA-SWCNT nanocomposites of NLC decreases compared to pure NLC. A fast response time is observed with an increase in the concentration of ODA-SWCNT in NLC host. Additionally, optical response of pure NLC in a twisted nematic (TN) cell fabricated using mixtures of polyimide (PI) and ODA-SWCNT as an alignment layer is investigated. The optical response time decreased by ~75% in a TN cell fabricated with a mixture of PI and ODA-SWCNT compared to that of a TN cell prepared using a pure PI alignment layer. The presence of ODA-SWCNT in the alignment layer enhances the surface anchoring of the NLC molecules leading to an increase in the elastic constant and a decrease in the optical response time of NLC.     

Water-soluble carbosilane dendrimers protect phosphorothioate oligonucleotides from binding to serum proteins

Treatment of dendriplexes formed between water-soluble carbosilane dendrimers and phosphorothioate oligodeoxynucleotides (ODN) with the anionic detergent sodium dodecyl sulfate disrupted the complexes indicating that the nature of the union in such dendriplexes is merely electrostatic. However, dendriplexes were not dissociated by serum proteins like bovine or human serum albumins, as assessed by gel electrophoresis and fluorescence experiments. This would imply a dendrimer-mediated protective effect able to prevent ODN interactions with serum proteins and additionally could translate into a reduction of the ODN doses needed to achieve the biological effects. The employment of carbosilane dendrimers as carriers may solve the problem of ODN kidnapping by plasmatic proteins as a key drawback for therapeutics involving ODNs. As examples, transfection processes on normal primary peripheral blood cells and diagnosis of HIV infection in the presence of serum have been assayed.     

Improvement deoxyribo nucleic acid spots classification in polyacrylamide [correction of polyacrilamide] gel images using photometric normalization algorithms

A comparative study of four enhancement algorithms traditionally used in computer vision for photometric normalization of images affected by illumination changes is presented in this paper. We experimented with the performance of these approaches to reduce the low frequency multiplicative noise that is produced as a result of a non-homogeneity illumination or a non-homogeneity developed chemical process in polyacrylamide gel electrophoresis images for the purpose of automatic classification of deoxyribo nucleic acid (DNA). The algorithms are tested on a database and their results are compared in a system for feature extraction and DNA classification.     

Water-soluble carbosilane dendrimers: synthesis biocompatibility and complexation with oligonucleotides; evaluation for medical applications

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.