Enhanced two-photon absorption with novel octupolar propeller-shaped fluorophores derived from triphenylamine

[structure: see text] Novel octupolar fluorophores derived from the symmetrical functionalization of a triphenylamine core with strong acceptor peripheral groups via phenylene-ethynylene linkers have been synthesized and shown to exhibit high fluorescence quantum yields, very large TPA cross-sections in the red-NIR region, and suitable photostability.     

Massive docking of flexible ligands using environmental niches in parallelized genetic algorithms

Virtual screening of large libraries of small compounds requires fast and reliable automatic docking methods. In this article we present a parallel implementation of a genetic algorithm (GA) and the implementation of an enhanced genetic algorithm (EGA) with niching that lead to remarkable speedups compared to the original version AutoDock 3.0. The niching concept is introduced naturally by sharing genetic information between evolutions of subpopulations that run independently, each on one CPU. A unique set of additionally introduced search parameters that control this information flow has been obtained for drug‐like molecules based on the detailed study of three test cases of different complexity. The average docking time for one compound is of 8.6 s using eight R10,000 processors running at 200 MHz in an Origin 2000 computer. Different genetic algorithms with and without local search (LS) have been compared on an equal workload basis showing EGA/LS to be superior over all alternatives because it finds lower energy solutions faster and more often, particularly for high dimensionality problems. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1971–1982, 2001     

An example of entropy balance in natural convection,Part 2: the thermodynamic Boussinesq equations

Numerical simulations of natural convection performed with the usual Boussinesq equations result in unbalanced irreversibility budget. The thermodynamic Boussinesq equations solve this problem, especially because they simulate production of kinetic energy within the fluid through its expansion and contraction. These fluid volume changes, without which natural convection would not occur, also induce heat transfer by piston effect. The piston effect, which appears then as an intrinsic component of buoyancy-induced natural convection, introduces the non-dimensional adiabatic temperature gradient as a control parameter of natural convection. To cite this article: M. Pons, P. Le Quéré, C. R. Mecanique 333 (2005).     

UV/TiO2 Photocatalytic Degradation of Xanthene Dyes

UV/titanium dioxide (TiO₂) degradation of two xanthene dyes, erythrosine B (Ery) and eosin Y (Eos), was studied in a photocatalytic reactor. Photocatalysis was able to degrade 98% of Ery and 73% of Eos and led to 65% of chemical oxygen demand removal. Experiments in buffered solutions at different initial pH values reveal the pH dependence of the process, with better results obtained under acidic conditions due to the electrostatic attraction caused by the opposite charges of TiO₂ (positive) and of anionic dyes (negative). Batch activity tests under methanogenic conditions showed the high toxicity exerted by the dyes even at low concentrations (~85% with initial concentration of 0.3 mmol L^?1), but the end products of photocatalytic treatment were much less toxic toward methanogenic bacteria, as detoxification of 85 ± 5% for Eos and 64 ± 7% for Ery were obtained. In contrast, the dyes had no inhibitory effect on the biogenic‐carbon biodegradation activity of aerobic biomass, obtained by respirometry. The results demonstrate that photocatalysis combining UV/TiO₂ as a pretreatment followed by an anaerobic biological process may be promising for the treatment of wastewaters produced by many industries.     

Enhancing the stability and biological functionalities of quantum dots via compact multifunctional ligands

We have designed and synthesized a series of modular ligands based on poly(ethylene glycol) (PEG) coupled with functional terminal groups to promote water-solubility and biocompatibility of quantum dots (QDs). Each ligand is comprised of three modules: a PEG single chain to promote hydrophilicity, a dihydrolipoic acid (DHLA) unit connected to one end of the PEG chain for strong anchoring onto the QD surface, and a potential biological functional group (biotin, carboxyl, and amine) at the other end of the PEG. Water-soluble QDs capped with these functional ligands were prepared via cap exchange with the native hydrophobic caps. Homogeneous QD solutions that are stable over extended periods of time and over a broad pH range were prepared. Surface binding assays and cellular internalization and imaging showed that QDs capped with DHLA-PEG-biotin strongly interacted with either NeutrAvidin immobilized on surfaces or streptavidin coupled to proteins which were subsequently taken up by live cells. EDC coupling in aqueous buffer solutions was also demonstrated using resonance energy transfer between DHLA-PEG-COOH-functionalized QDs and an amine-terminated dye. The new functional surface ligands described here provide not only stable and highly water-soluble QDs but also simple and easy access to various biological entities.     

Cationic oligonucleotide-peptide conjugates with aggregating properties enter efficiently into cells while maintaining hybridization properties and enzymatic recognition

Oligonucleotide delivery is a crucial issue for therapeutical purposes and is often addressed by conjugation to short cationic peptides although with controversial results. To further examine this mechanism, a 15-mer anionic oligonucleotide was conjugated to a cationic peptide in order to obtain a diblock compound with an overall positive charge with aggregation properties. These microaggregates were efficiently internalized in cells via the expeditious pathway used by commercial gene delivery systems. Moreover, stability of the duplex formed with the complementary sequence increased without inhibiting oligonucleotide enzyme recognition as shown by the properties of the conjugate to prime chain elongation by Taq DNA polymerase in a linear amplification/sequencing process.     

Compact differences of composition operators on weighted Dirichlet spaces

Here we consider when the difference of two composition operators is compact on the weighted Dirichlet spaces . Specifically we study differences of composition operators on the Dirichlet space and S ², the space of analytic functions whose first derivative is in H ², and then use Calderón’s complex interpolation to extend the results to the general weighted Dirichlet spaces. As a corollary we consider composition operators induced by linear fractional self-maps of the disk.     

Unconventional acceptor and donor functional groups linked by a captodative spacer

The chemical stability to oxidation of a set of compounds built up from acceptor and donor submits linked by a methylene or a hydroxymethylene group was studied. Whereas 1-butyl-3-[1,2,4-triazol-5(3)-ylmethyl]pyridinium salts 2d,e showed high stability to oxidation, 1-butyl-4-[imidazol-4(5)-ylhidroxymethyl]pyridinium salt 14f was oxidised spontaneously to the corresponding carbonyl compound, indicating the capability of the oxidation phenomenon to be controlled by the nature of the building blocks.     

World-lines,poincaré realisations and predictive relativistic mechanics

The conditions putting a given family of world-lines into the scheme of predictive relativistic mechanics are studied. Examples are given of the wide class of models satisfying such conditions.