Visible-Light-Mediated Charge Transfer Enables C−C Bond Formation with Traceless Acceptor Groups

The development and application of traceless acceptor groups in photochemical C−C bond formation is described. This strategy was enabled by the photoexcitation of electron donor–acceptor (EDA) complexes with visible light. The traceless acceptors, which were readily prepared from amino acid and peptide feedstocks, could be used to alkylate a wide range of heteroarene and enamine donors under metal- and peroxide-free conditions. The crucial role of the EDA complexes in the mechanism of these reactions was explored through combined experimental and computational studies

Photosensitized intermolecular carboimination of alkenes through the persistent radical effect

An intermolecular, two‐component vicinal carboimination of alkenes has been accomplished by energy transfer catalysis. Oxime esters of alkyl carboxylic acids were used as bifunctional reagents to generate both alkyl and iminyl radicals. Subsequently, addition of the alkyl radical to an alkene generates a transient radical for selective radical–radical cross‐coupling with the persistent iminyl radical. Furthermore, this process provides direct access to aliphatic primary amines and α‐amino acids by simple hydrolysis

Energy transfer catalysis mediated by visible light : principles, applications, directions

Harnessing visible light to access excited (triplet) states of organic compounds can enable impressive reactivity modes. This tutorial review covers the photophysical fundamentals and most significant advances in the field of visible-light-mediated energy transfer catalysis within the last decade. Methods to determine excited triplet state energies and to characterize the underlying Dexter energy transfer are discussed. Synthetic applications of this field, divided into four main categories (cyclization reactions, double bond isomerizations, bond dissociations and sensitization of metal complexes), are also examined

Single Bead Labeling Method for Combining Confocal Fluorescence On-Bead Screening and Solution Validation of Tagged One-Bead One-Compound Libraries

SummaryScreening of one-bead one-compound libraries by incubating beads with fluorescently labeled target protein requires isolation and structure elucidation of a large number of primary hit beads. However, the potency of the identified ligands is only revealed after time consuming and expensive larger scale resynthesis and testing in solution. Often, many of the resynthesized compounds turn out to be weak target binders in solution due to large differences between surface and solution binding affinities. For an industry style high-throughput screening (HTS) process a high false positive rate is detrimental. We have therefore combined single bead and single molecule/single cell techniques into an integrated HTS process in which the picomole amount of substance contained on one isolated hit bead is sufficient for quality control, structure determination, and precise affinity determination to the target protein in solution

Lattice Boltzmann simulations of soft matter systems

This article concerns numerical simulations of the dynamics of particles immersed in a continuum solvent. As prototypical systems, we consider colloidal dispersions of spherical particles and solutions of uncharged polymers. After a brief explanation of the concept of hydrodynamic interactions, we give a general overview over the various simulation methods that have been developed to cope with the resulting computational problems. We then focus on the approach we have developed, which couples a system of particles to a lattice Boltzmann model representing the solvent degrees of freedom. The standard D3Q19 lattice Boltzmann model is derived and explained in depth, followed by a detailed discussion of complementary methods for the coupling of solvent and solute. Colloidal dispersions are best described in terms of extended particles with appropriate boundary conditions at the surfaces, while particles with internal degrees of freedom are easier to simulate as an arrangement of mass points with frictional coupling to the solvent. In both cases, particular care has been taken to simulate thermal fluctuations in a consistent way. The usefulness of this methodology is illustrated by studies from our own research, where the dynamics of colloidal and polymeric systems has been investigated in both equilibrium and nonequilibrium situations.Comment: Review article, submitted to Advances in Polymer Science. 16 figures, 76 page

HyMeX: A 10-Year Multidisciplinary Program on the Mediterranean Water Cycle

Drobinski, P. ... et. al.-- 20 pages, 10 figures, 1 table, supplement material http://journals.ametsoc.org/doi/suppl/10.1175/BAMS-D-12-00244.1HyMeX strives to improve our understanding of the Mediterranean water cycle, its variability from the weather-scale events to the seasonal and interannual scales, and its characteristics over one decade (2010–20), with a special focus on hydrometeorological extremes and the associated social and economic vulnerability of the Mediterranean territoriesHyMeX was developed by an international group of scientists and is currently funded by a large number of agencies. It has been the beneficiary of financial contributions from CNRS; Météo-France; CNES; IRSTEA; INRA; ANR; Collectivité Territoriale de Corse; KIT; CNR; Université de Toulouse; Grenoble Universités; EUMETSAT; EUMETNET; AEMet; Université Blaise Pascal, Clermont Ferrand; Université de la Méditerranée (Aix-Marseille II); Université Montpellier 2; CETEMPS; Italian Civil Protection Department; Université Paris- Sud 11; IGN; EPFL; NASA; New Mexico Tech; IFSTTAR; Mercator Ocean; NOAA; ENEA; TU Delft; CEA; ONERA; IMEDEA; SOCIB; ETH; MeteoCat; Consorzio LAMMA; IRD; National Observatory of Athens; Ministerio de Ciencia e Innovación; CIMA; BRGM; Wageningen University and Research Center; Department of Geophysics, University of Zagreb; Institute of Oceanography and Fisheries, Split, Croatia; INGV; OGS; Maroc Météo; DHMZ; ARPA Piemonte; ARPA-SIMC Emilia-Romagna; ARPA Calabria; ARPA Friuli Venezia Giulia; ARPA Liguria; ISPRA; University of Connecticut; Università degli Studi dell'Aquila; Università di Bologna; Università degli Studi di Torino; Università degli Studi della Basilicata; Università La Sapienza di Roma; Università degli Studi di Padova; Università del Salento; Universitat de Barcelona; Universitat de les Illes Balears; Universidad de Castilla-La Mancha; Universidad Complutense de Madrid; MeteoSwiss; and DLR. It also received support from the European Community's Seventh Framework Programme (e.g., PERSEUS, CLIM-RUN)Peer reviewe

Iota-Carrageenan Is a Potent Inhibitor of Influenza A Virus Infection

The 2009 flu pandemic and the appearance of oseltamivir-resistant H1N1 influenza strains highlight the need for treatment alternatives. One such option is the creation of a protective physical barrier in the nasal cavity. In vitro tests demonstrated that iota-carrageenan is a potent inhibitor of influenza A virus infection, most importantly also of pandemic H1N1/2009 in vitro. Consequently, we tested a commercially available nasal spray containing iota-carrageenan in an influenza A mouse infection model. Treatment of mice infected with a lethal dose of influenza A PR8/34 H1N1 virus with iota-carrageenan starting up to 48 hours post infection resulted in a strong protection of mice similar to mice treated with oseltamivir. Since alternative treatment options for influenza are rare, we conclude that the nasal spray containing iota-carrageenan is an alternative to neuraminidase inhibitors and should be tested for prevention and treatment of influenza A in clinical trials in humans

Visible-light-photosensitized aryl and alkyl decarboxylative functionalization reactions

Despite significant progress in aliphatic decarboxylation, an efficient and general protocol for radical aromatic decarboxylation has lagged far behind. Herein, we describe a general strategy for rapid access to both aryl and alkyl radicals by photosensitized decarboxylation of the corresponding carboxylic acids esters followed by their successive use in divergent carbon–heteroatom and carbon–carbon bond‐forming reactions. Identification of a suitable activator for carboxylic acids is the key to bypass a competing single‐electron‐transfer mechanism and “switch on” an energy‐transfer‐mediated homolysis of unsymmetrical σ‐bonds for a concerted fragmentation/decarboxylation process

Visible-Light Photosensitized Aryl and Alkyl Decarboxylative Carbon-Heteroatom and Carbon-Carbon Bond Formations

A general strategy to access both aryl and alkyl radicals by photosensitized decarboxylation of the corresponding carboxylic acids esters has been developed. An energy transfer mediated homolysis of unsymmetrical sigma-bonds for a concerted fragmentation/decarboxylation process is involved. As a result, an independent aryl/alkyl radical generation step enables a series of key C-X and C-C bond forming reactions by simply changing the radical trapping agent.</sub