Multienzymatic preparation of 3-[(1R)-1-hydroxyethyl]benzoic acid and (2S)-hydroxy(phenyl)ethanoic acid

The use of two oxidoreductases (an aldoketo reductase from Escherichia coli JM109 and an alcohol dehydrogenase from Lactobacillus brevis) has demonstrated that it is possible to prepare enatiomerically pure diols in a one-pot operation. The reactions were applied to the synthesis of (1R)-1-[3-(hydroxymethyl)phenyl]ethanol and (1S)-1-phenylethane-1,2-diol, using a two-step procedure. The yield is nearly quantitative and the enantiomeric purity is greater than 95%. A third step has been introduced by adding a cell biocatalyst showing dihydrodiol dehydrogenase activity from Pseudomonas fluorescens N3. This allows for the preparation of 3-[(1R)-1-hydroxyethyl]benzoic acid and (2S)-hydroxy(phenyl)ethanoic acid.     

Homogeneous and heterogeneous olefin epoxidation catalyzed by a binuclear Mn(II)Mn(III) complex

The synthesis and characterization of a binuclear carboxylated bridged manganese complex containing the heptadentate ligand N,N′-bis(2-hydroxybenzyl)-N,N′-bis(2-methylpyridyl)-2-ol-1,3-propanediamine (H₃bbppnol) is reported. This complex was characterized by elemental analysis; infrared, electronic (UV–vis) and EPR spectroscopy; and conductivity measurements. The complex was immobilized on silica by either adsorption or entrapment via a sol–gel route. The obtained solids were characterized by thermogravimetric analyses (TG and DSC), UV–vis and infrared spectroscopy, and X-ray diffraction. The catalytic performance of the binuclear manganese complex in epoxidation reactions was evaluated for both homogeneous and heterogeneous systems. The catalytic investigation revealed that the complex performs well as an epoxidation catalyst for the substrates cyclohexene (26–39%) and cyclooctene (29–74%). The solids containing the immobilized complex can be recovered from the reaction medium and reused, maintaining good catalytic activity.     

Crystalline protein domains and lipid bilayer vesicle shape transformations

Cellular membranes can take on a variety of shapes to assist biological processes including endocytosis. Membrane-associated protein domains provide a possible mechanism for determining membrane curvature. We study the effect of tethered streptavidin protein crystals on the curvature of giant unilamellar vesicles (GUVs) using confocal, fluorescence, and differential interference contrast microscopy. Above a critical protein concentration, streptavidin domains align and percolate as they form, deforming GUVs into prolate spheroidal shapes in a size-dependent fashion. We propose a mechanism for this shape transformation based on domain growth and jamming. Osmotic deflation of streptavidin-coated GUVs reveals that the relatively rigid streptavidin protein domains resist membrane bending. Moreover, in contrast to highly curved protein domains that facilitate membrane budding, the relatively flat streptavidin domains prevent membrane budding under high osmotic stress. Thus, crystalline streptavidin domains are shown to have a stabilizing effect on lipid membranes. Our study gives insight into the mechanism for protein-mediated stabilization of cellular membranes.     

Expected reliability of communication protocols

We consider the problem of sending a message from a sender $s$ to a receiver $r$ through an unreliable network by specifying in a protocol what each vertex is supposed to do if it receives the message from one of its neighbors. A protocol for routing a message in such a graph is finite if it never floods $r$ with an infinite number of copies of the message. The expected reliability of a given protocol is the probability that a message sent from $s$ reaches $r$ when the edges of the network fail independently with probability $1?p$.We discuss, for given networks, the properties of finite protocols with maximum expected reliability in the case when $p$ is close to 0 or 1, and we describe networks for which no one protocol is optimal for all values of $p$. In general, finding an optimal protocol for a given network and fixed probability is challenging and many open problems remain.     

Synthesis of crosslinked nanostructured saccharidic vinyl copolymers and their functionalization

Saccharidic monomers and a macromonomer were synthesized and copolymerized in the presence of divinylbenzene (DVB) as crosslinker in conditions of separation of phases to give hydrophilic nanostructured sugar-based vinyl copolymers. Appropriate model molecules such as N-benzyl-d-gluconamide for the saccharidic copolymers and 4-(4-chlorobutoxy)benzaldehyde and (E)-4-(4-chloro-2-butenyloxy)benzaldehyde for electrophilic reagents prefiguring possible copper amine oxidase inhibitors allowed identification of conditions for useful monofunctionalizations mainly at the position 2 of the saccharidic units. The examined samples of the nanostructured copolymers from one of the monomers proved to be stable enough to tolerate the functionalization reactions without loss of morphology.     

Chemoenzymatic synthesis of conduritol analogues

Several conduritol and conduramine analogues have been synthesized from β-substituted naphthalenes via a chemoenzymatic approach, in a high regio- and stereocontrolled way.