C-Phosphorylation of Electron-Rich Heterocycles

Abstract

C-phosphorylation of pyrrole, furan, thiophene derivatives and their benzanalogs by phosphorus tribromide has been studied. Perspective methods for involving trivalent phosphorus residues at a different position of the rings have been developed. Unknown early the heterocycle's derivatives with tri- and tetracoordinated phosphorus substituents (1–5) and novel types of phosphoruscontaining heterocycles (6,7) have been obtained.     

Production of Antibodies and Development of Specific Polarization Fluoroimmunoassay for Acetochlor

Specific polyclonal antibodies towards acetochlor (2-chloro- N -(ethoxymethyl)- N -(2-ethyl-6-methylphenyl)acetamide) were obtained from rabbits immunized against a 3-mercaptopropionic acid derivative of acetochlor, covalently attached to bovine serum albumin. A polarization fluoroimmuoassay (PFIA) based on these antibodies was developed and optimized to detect acetochlor in water samples. The optimized PFIA had a detection limit of 9 µg/L, linear working range from 50 to 5500 µg/L and within-assay coefficient of variation less than 4%. Cross-reactivity studies demonstrated that these antibodies are capable of specific detection of acetochlor amongst structurally related chloroacetanilide herbicides. Assay cross-reactivity values were: alachlor 0%, metolachlor 2.4%, propachlor 0%, butachlor 0.2% and dimethachlor 0.5%. Five organic solvents commonly used in sample extraction were evaluated for their effect on acetochlor PFIA performance, and methanol and ethanol were found to be compatible with the assay up to 10% v/v.     

Cationic polymerization of isobutylene at room temperature

This review highlights recent approaches toward polyisobutylene (PIB) by an energy efficient room temperature cationic polymerization. Special focus is laid on our own work using modified Lewis acids and nitrile‐ligated metal complexes associated with weakly coordinating anions. In both cases, suitable conditions have been found for efficient production of PIB characterized by medium to low molar masses and a high content of exo double bonds as end groups—the typical features of highly reactive PIB, an important commercial intermediate toward oil and gasoline additives. These and other approaches demonstrate that the cationic polymerization of isobutylene is still not fully explored, and new innovative catalyst systems can lead to surprising results of high commercial interest. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Functionalization of Metal–Organic Frameworks through the Postsynthetic Transformation of Olefin Side Groups

For the first time, the adaptability of the C?C double bond as a versatile precursor for the postsynthetic modification (PSM) of microporous materials was extensively investigated and evaluated. Therefore, an olefin‐tagged 4,4′‐bipyridine linker was synthesized and successfully introduced as pillar linker within a 9,10‐triptycenedicarboxylate (TDC) zinc paddle‐wheel metal–organic framework (MOF) through microwave‐assisted synthesis. Different reactions, predominately used in organic chemistry, were tested, leading to the development of new postsynthetic reactions for the functionalization of solid materials. The postsynthetic oxidation of the olefin side groups applying osmium tetroxide (OsO₄) as a catalyst led to the formation of a microporous material with free vicinal diol functionalities. The epoxidation with dimethyldioxirane (DMDO) enabled the synthesis of epoxy‐functionalized MOFs. In addition to that, reaction procedures for a postsynthetic hydroboration with borane dimethyl sulfide as well as a photoinduced thiol–ene click reaction with ethyl mercaptan were developed. For all of these PSMs, yields of more than 90 % were obtained, entirely maintaining the crystallinity of the MOFs. Since the direct introduction of the corresponding groups by means of pre‐synthetic approaches is hardly possible, these new PSMs are useful tools for the functionalization of porous solids towards applications such as selective adsorption, separation, and catalysis.     

Rapid determination of RMSDs corresponding to macromolecular rigid body motions

Finding the root mean sum of squared deviations (RMSDs) between two coordinate vectors that correspond to the rigid body motion of a macromolecule is an important problem in structural bioinformatics, computational chemistry, and molecular modeling. Standard algorithms compute the RMSD with time proportional to the number of atoms in the molecule. Here, we present RigidRMSD, a new algorithm that determines a set of RMSDs corresponding to a set of rigid body motions of a macromolecule in constant time with respect to the number of atoms in the molecule. Our algorithm is particularly useful for rigid body modeling applications, such as rigid body docking, and also for high‐throughput analysis of rigid body modeling and simulation results. We also introduce a constant‐time rotation RMSD as a similarity measure for rigid molecules. A C++ implementation of our algorithm is available at http://nano‐d.inrialpes.fr/software/RigidRMSD . © 2014 Wiley Periodicals, Inc.     

Chemo- and regioselective oxidation of substituted 2,3,4,9-tetrahydro-1H-carbazoles

Chemistry of Heterocyclic Compounds - Chemo- and regioselective oxidation of substituted 2,3,4,9-tetrahydro-1H-carbazoles was used to obtain 2,3,4,9-tetrahydro-1H-carbazol-1-ones or...     

Nonvolatile memory elements based on the intercalation of organic molecules inside carbon nanotubes

We propose a novel class of nonvolatile memory elements based on the modification of the transport properties of a conducting carbon nanotube by the presence of an encapsulated molecule. The guest molecule has two stable orientational positions relative to the nanotube that correspond to conducting and nonconducting states. The mechanism, governed by a local gating effect of the molecule on the electronic properties of the nanotube host, is studied using density functional theory. The mechanisms of reversible reading and writing of information are illustrated with a F4TCNQ molecule encapsulated inside a metallic carbon nanotube. Our results suggest that this new type of nonvolatile memory element is robust, fatigue-free, and can operate at room temperature.     

Highly dispersive large mode area photonic bandgap fiber

An all-silica photonic bandgap fiber composed of a low-index core surrounded by alternating high- and low-index rings allows us to achieve a large mode area (500 microm(2)) and large chromatic dispersion. Sharp resonances from the even Bragg mode to odd ring modes theoretically lead to 20,000 ps/(nm km) chromatic dispersion when large bends are applied. By nature, sharp resonances are sensitive to inhomogeneities along the fiber length. Under experimental conditions, the resonances are broadened and the dispersion coefficient is decreased to 1000 ps/(nm km). However, to the best of our knowledge, this is the largest dispersion coefficient reported using a large mode area fiber.