Enantioselective Linchpin Catalysis by SOMO Catalysis: An Approach to the Asymmetric α‐Chlorination of Aldehydes and Terminal Epoxide Formation

Time for SOme MOre : For the first time SOMO (singly occupied molecular orbital) activation has been exploited to allow a new approach to the α‐chlorination of aldehydes. This transformation can be readily implemented as part of a linchpin catalysis approach to the enantioselective production of terminal epoxides.

     

Extension groups between simple Mackey functors

In order to better understand the structure of indecomposable projective Mackey functors, we study extension groups of degree 1 between simple Mackey functors. We explicitly determine these groups between simple functors indexed by distinct normal subgroups. We next study the conditions under which it is possible to restrict ourselves to that case, and we give methods for calculating extension groups between simple Mackey functors which are not indexed by normal subgroups. We then focus on the case where the simple Mackey functors are indexed by the same subgroup. In this case, the corresponding extension group can be embedded in an extension group between modules over a group algebra, and we describe the image of this embedding. In particular, we determine all extension groups between simple Mackey functors for a p-group and for a group that has a normal p-Sylow subgroup. Finally, we compute higher extension groups between simple Mackey functors for a group that has a p-Sylow subgroup of order p.     

On the role of the bridging dicyanamidobenzene ligand in a new binuclear ruthenium complex: [{Ru(tpy)(thd)}2(mu-dicyd)][PF6] with tpy = 2,2':6',2' '-terpyridine and thd = 2,2,6,6-tetramethyl-3,5-heptanedione

The dicyanamidobenzene-bridge diruthenium complex [{Ru(tpy)(thd)}(2)(mu-dicyd)][PF(6)] ([3][PF(6)]) (dicyd = 1,4-dicyanamidobenzene, tpy = 2,2':6',2' '-terpyridine, thd = 2,2,6,6-tetramethyl-3,5-heptanedione) and its mononuclear counterpart [Ru(tpy)(thd)(Ipcyd)] (2) [Ipcyd = 4-iodophenylcyanamide anion (Ipcyd(-))] were synthesized and fully characterized. Cyclic voltammetry of 3 showed the presence of four reversible one-electron redox couples. UV-vis-NIR spectroelectrochemistry and EPR spectroscopy of the electrogenerated paramagnetic intermediates were used to ascertain the oxidation-state distribution. The stable starting dinuclear complex 3(+) is found to be a ligand-centered anion radical as shown by EPR spectroscopy, magnetic susceptibility measurements, and DFT calculations. Oxidation of 3(+) to 3(2+) led to an EPR silent system due to substantial intramolecular antiferromagnetic interaction of the electron spins carried by the low spin ruthenium(III) atom and the bridging anion radical dicyanamido (dicyd(*)(-)), an observation which was supported by UV-vis-NIR, X-ray structure, and DFT calculations. Complex 3(3+) presented an EPR spectra consistent with a total effective spin S = (1)/(2) issued from an antiferromagnetic interaction of electron spins carried by two low spin ruthenium(III) atoms and the bridging anion radical dicyd(*)(-) in accordance with UV-vis-NIR. This study shows that the dicyanamidobenzene bridging ligand has indubitably a noninnocent behavior.     

Synthesis of quantum dot-tagged submicrometer polystyrene particles by miniemulsion polymerization

Submicrometer fluorescent polystyrene (PS) particles have been synthesized via miniemulsion polymerization using CdSe/ZnS core-shell quantum dots (QDs). The influence of QD concentration, QD coating (either trioctylphosphine oxide (TOPO)-coated or vinyl-functionalized), and surfactant concentration on the polymerization kinetics and the photoluminescence properties of the prepared particles has been analyzed. Polymerization kinetics were not altered by the presence of QDs, whatever their surface coating. Latexes exhibited particle sizes ranging from 100 to 350 nm, depending on surfactant concentration, and a narrow particle size distribution was obtained in all cases. The fluorescence signal of the particles increased with the number of incorporated TOPO-coated QDs. The slight red shift of the emission maximum was correlated with phase separation between PS and QDs, which occurred during the polymerization, locating the QDs in the vicinity of the particle/water interface. QD-tagged particles displayed higher fluorescence intensity with TOPO-coated QDs compared to those with the vinyl moiety. The obtained fluorescent particles open up new opportunities for a variety of applications in biotechnology.     

Identification of the elastic properties of an artificial capsule membrane with the compression test: effect of thickness

The mechanical properties of a capsule membrane are evaluated by means of a compression experiment between two parallel plates. Since large deformations of the membrane are involved, the choice of the wall material constitutive law is essential. In this paper, we explore different classical laws to describe the behavior of the membrane and evaluate also the limit of application of the thin shell approximation. A numerical study of the compression process is performed using Abaqus software and an inverse method is used to identify the material constants of the constitutive laws. The comparison between the model predictions and experimental measurements on capsules with serum albumin-alginate membranes, indicates that the thin shell approximation is valid only for thickness to radius ratios up to 5% and that thick membranes obey non linear elastomer type constitutive laws. The Young modulus of the membrane material is found to increase non-linearly with membrane thickness, thus indicating that fabrication of thicker serum albumin-alginate walls results in capsules stiffer than expected.     

A new highly versatile handle for chemistry on a solid support: the pipecolic linker

The versatility of the pipecolic linker (Pip-linker) is illustrated by the synthesis of modified amino acids, C-terminal-modified pseudopeptides, and cyclic peptides, through side-chain anchoring of a lysine residue. Introduction of the first residue was easily accomplished and the Pip-linker revealed to be robust enough to support various chemical modifications.     

Controlling spin-spin network dynamics by repeated projective measurements

We show that coupled-spin network manipulations can be made highly effective by repeated projections of the evolving quantum states onto diagonal density-matrix states (populations). As opposed to the intricately crafted pulse trains that are often used to fine-tune a complex network's evolution, the strategy hereby presented derives from the "quantum Zeno effect" and provides a highly robust route to guide the evolution by destroying all unwanted correlations (coherences). We exploit these effects by showing that a relaxationlike behavior is endowed to polarization transfers occurring within a N-spin coupled network. Experimental implementations yield coupling constant determinations for complex spin-coupling topologies, as demonstrated within the field of liquid-state nuclear magnetic resonance.     

Hydromechanical Modelling of Experimentally Compacted Saturated Argillaceous Porous Media

In order to model the experimental compaction of clays as completely as possible, it is necessary to use the hydromechanical coupled three-dimensional theory for saturated porous media. The proposed formulation is based on elastoplasticity, more precisely on modified Cam-clay model. The identification of the parameters of the model is made by special oedometric experiments at steady state. The compaction experiments are simulated with accuracy in transient and steady states and complement those obtained in a recent study based only on steady state.     

Combining Steric and Electrostatic Stabilization Using Hydrophilic MacroRAFT Agents in an Ab Initio Emulsion Polymerization of Styrene

Hydrophilic (co)polymers carrying a thiocarbonyl thio end group such as poly(dimethylaminoethyl methacrylate), poly(ethylene oxide), and poly(ethylene oxide)‐block‐poly(dimethylaminoethyl methacrylate) have been evaluated as precursors of stabilizers in batch ab initio emulsion polymerization of styrene under acidic conditions to form electrosterically stabilized polystyrene latex particles. As a mixture of P(DMAEMA/H⁺Cl⁻)‐RAFT and PEO‐RAFT failed to give satisfactory results, PEO‐RAFT was used as a control agent for the RAFT polymerization of DMAEMA, and the resulting block copolymer was successfully used in ab initio styrene emulsion polymerization.

     

Generalized Solvable Structures and First Integrals for ODEs Admitting an Symmetry Algebra

The notion of solvable structure is generalized in order to exploit the presence of an algebra of symmetries for a kth-order ordinary differential equation with k > 3. In this setting, the knowledge of a generalized solvable structure for allows us to reduce to a family of second-order linear ordinary differential equations depending on k ? 3 parameters. Examples of explicit integration of fourth and fifth order equations are provided in order to illustrate the procedure.