Presence Of Organic Hydroperoxides Research Articles

Mo(VI) Complexes Immobilized on SBA-15 as an Efficient Catalyst for 1-Octene Epoxidation

SBA-15 materials were functionalized through a post-synthetic methodology with molybdenum-Schiff bases to provide catalytic activity in epoxidation reactions. Thus, glycidoxypropyl functionalities were first attached to the surface of the mesostructured silica, followed by the reaction of the immobilized oxirane groups with 2-amino propyl pyridine. This reaction allowed the obtaining of (hydroxypropyl)-2-aminomethyl pyridine ligands, directly tethered to the surface of the mesoporous silica-based SBA-15, which resulted in excellent chelating ligands to immobilize dioxo molydenum species by a reaction with MoO2(acac)2. This investigation comprises a thorough characterization of the process for building the immobilized molybdenum-Schiff base complexes, as well as the use of the obtained materials in 1-octene oxidation in the presence of organic hydroperoxides. These materials displayed high intrinsic catalytic activity in the epoxidation of 1-octene with organic hydroperoxides under a wide variety of conditions, although both the reaction solvent as well as the nature of the organic hydroperoxide, exerted a dramatic influence on the catalytic activity of these heterogeneous oxidation catalysts. Thus, whereas nonpolar solvents provided good epoxide yields with high efficiency in the use of the oxidant, polar solvents depressed the catalytic activity of the supported Mo-Schiff bases. These results have been ascribed to the competition with the solvent, when polar, for binding to the metal sites, thus avoiding the formation of the hydroperoxo-metal cycle and the epoxidation of the olefin. The catalysts presented here show good reusability with low catalytic activity decay after the first reuse.

Immobilization of monomeric organometallic molybdenum oxo and carbonyl complexes and their application in epoxidation reactions

Various oxomolybdenum complexes are efficient and selective homogeneous catalysts in the presence of organic hydroperoxides. The increasing interest in the heterogenisation of such catalysts has led to an increased interest in finding suitable support materials for the complexes. These supports include ionic liquids, mesoporous materials and zeolites to name a few. Several methods are used to anchor the catalyst depending on the nature of the carrier material. The supported catalysts combine properties of homogeneous catalysts such as reactivity, control and selectivity with those of heterogeneous catalysts such as enhanced stability and recyclability.

The Rhizobium etli cyaC product: characterization of a novel adenylate cyclase class.

Adenylate cyclases (ACs) catalyze the formation of 3',5'-cyclic AMP (cAMP) from ATP. A novel AC-encoding gene, cyaC, was isolated from Rhizobium etli by phenotypic complementation of an Escherichia coli cya mutant. The functionality of the cyaC gene was corroborated by its ability to restore cAMP accumulation in an E. coli cya mutant. Further, overexpression of a malE::cyaC fusion protein allowed the detection of significant AC activity levels in cell extracts of an E. coli cya mutant. CyaC is unrelated to any known AC or to any other protein exhibiting a currently known function. Thus, CyaC represents the first member of a novel class of ACs (class VI). Hypothetical genes of unknown function similar to cyaC have been identified in the genomes of the related bacterial species Mesorhizobium loti, Sinorhizobium meliloti, and Agrobacterium tumefaciens. The cyaC gene is cotranscribed with a gene similar to ohr of Xanthomonas campestris and is expressed only in the presence of organic hydroperoxides. The physiological performance of an R. etli cyaC mutant was indistinguishable from that of the wild-type parent strain both under free-living conditions and during symbiosis.

The OhrR repressor senses organic hydroperoxides by reversible formation of a cysteine-sulfenic acid derivative.

Reactive oxygen species induce the expression of detoxification and repair genes critical for life in an aerobic environment. Bacterial factors that sense reactive oxygen species use either thiol-disulfide exchange reactions (OxyR, RsrA) or redox labile 2Fe-2S clusters (SoxR). We demonstrate that the reduced form of Bacillus subtilis OhrR binds cooperatively to two adjacent inverted repeat sequences in the ohrA control region and thereby represses transcription. In the presence of organic hydroperoxides, OhrR is inactivated by the reversible oxidation of a single conserved cysteine residue to the corresponding cysteine-sulfenic acid, and perhaps to higher oxidation states.

Modification of lignin for the production of new compounded materials.

The cell walls of woody plants are compounded materials made by in situ polymerization of a polyphenolic matrix (lignin) into a web of fibers (cellulose), a process that is catalysed by polyphenoloxidases (laccases) or peroxidases. The first attempt to transform the basic strategy of this natural process for use in human craftsmanship was the ancient lacquer method. The sap of the lacquer tree (Rhus verniciflua) contains large amounts of a phenol (urushiol), a polysaccharide and the enzyme laccase. This oil-in-water emulsion solidifies in the presence of oxygen. The Chinese began using this phenomenon for the production of highly creative artwork more than 6,000 years ago. It was the first example of an isolated enzyme being used as a catalyst to create an artificial plastic compound. In order to apply this process to the production of products on an industrial scale, an inexpensive phenol must be used, which is transferred by an enzyme to active radicals that react with different components to form a compounded material. At present, the following approaches have been studied: (1) In situ polymerization of lignin for the production of particle boards. Adhesive cure is based on the oxidative polymerization of lignin using phenoloxidases (laccase) as radical donors. This lignin-based bio-adhesive can be applied under conventional pressing conditions. The resulting particle boards meet German performance standards. By this process, 80% of the petrochemical binders in the wood-composite industry can be replaced by materials from renewable resources. (2) Enzymatic copolymerization of lignin and alkenes. In the presence of organic hydroperoxides, laccase catalyses the reaction between lignin and olefins. Detailed studies on the reaction between lignin and acrylate monomers showed that chemo-enzymatic copolymerization offers the possibility to produce defined lignin-acrylate copolymers. The system allows control of the molecular weights of the products in a way that has not been possible with chemical catalysts. This is a novel attempt to enzymatically induce grafting of polymeric side chains onto the lignin backbone, and it enables the utilization of lignin as part of new engineering materials. (3) Enzymatic activation of the middle-lamella lignin of wood fibers for the production of wood composites. The incubation of wood fibers with a phenol oxidizing enzyme results in oxidative activation of the lignin crust on the fiber surface. When such fibers are pressed together, boards are obtained which meet the German standards for medium-density fiber boards (MDF). The fibers are bound together in a way that comes close to that by which wood fibers are bound together in naturally grown wood. This process will, for the first time, yield wood composites that are produced solely from naturally grown products without any addition of resins.

Formation of hydroperoxides from nucleic acids by irradiation with x-rays in aqueous systems.

IN the course of our studies of the chemical effects of X-rays on nucleic acids in aqueous solutions1, we have had occasion to measure the amounts of peroxide produced. Two methods were employed: (a) the reaction with titanium sulphate reagent2 and spectrophotometric measurement of the resulting complex at 405 mµ ; (b) the oxidation of potassium iodide3 and determination of the liberated iodine (I3 −) by the absorption at 353 mµ. It was found that, in solutions of thymus deoxyribonucleic acid and also of yeast ribonucleic acid irradiated in the presence of oxygen, the yields of total peroxide, as determined by the iodide method, were always greater than those of hydrogen peroxide, estimated by titanium sulphate. This observation can be explained by the presence of organic hydroperoxides in the irradiated nucleate solutions, since it is known that hydro-peroxides will oxidize iodide ions, but do not give, in general, the coloured complex with the titanium sulphate reagent.