RESUMO
Amphiphilic and lipophilic donor-acceptor naphthalimide-oligothiophene assemblies exhibiting almost identical intramolecular properties, but differing in their intermolecular interactions, have been synthesized. Here we analyze the effect of replacing the normally used lipophilic alkyl chains with hydrophilic ones in directing molecular aggregation from an antiparallel to a parallel stacking. This different molecular packing of the amphiphilic, NIP-3TAmphi, and lipophilic, NIP-3TLipo, systems is assessed by electronic spectroscopies, scanning electronic microscopy and DFT quantum-chemical calculations. Theoretical calculations indicate that the presence of amphiphilic interactions promotes a face-to-face parallel arrangement of neighbor molecules, which induces improved electronic coupling and therefore enhances the charge transport ability and photoconducting properties of this type of materials. Time of flight and photoconducting measurements are used to determine the impact of the amphiphilic and lipophilic interactions on their possible performance in optoelectronic devices.
RESUMO
A new selective polymer has been developed (Patent: P201500704) with high mercury sorption capacity. The combination of this material with a Direct Mercury Analyser (DMA80) has overcome important limitations of this equipment for mercury determination of complex matrix samples, like high saline content, due to the ability of this material to selective and efficient mercury retention. Furthermore, application for fast screening of mercury species in food samples, like fish, is also presented. The polymer material has been synthesized by the precipitation technique, using Azobisisobutyronitrile (AIBN) as initiator, 2-(Methacryloylamino) ethyl 2-Methyl Acrylate (NOBE) as cross-linker, and 1-phenyl-3-(-3-vinyl phenyl) thiourea as monomer. It has been characterized by SEM, TGA, FTIR, and binding isotherms have been established through Langmuir and Freundlich models. Selectivity has been proven by carrying out cross-reactivity experiments.
RESUMO
A new polymeric material (Patent: P201400535) highly specific for mercury is presented. Its great capability to pre-concentrate and selectively elute inorganic mercury and methylmercury are the main figures of merit. The polymer can be reused several times. To our knowledge, this is the only polymer proposed in the literature for direct inorganic mercury and methylmercury speciation without need of chromatography or quantification by difference. The polymer formation is based on the reaction of a vinyl derivative of 8-hydroxiquinoline as monomer, and 2-(Methacryloylamino) ethyl 2-Methyl Acrylate (NOBE) as co-monomer. Random radical polymerization by the precipitation method was carried out using Azobisisobutyronitrile (AIBN) as initiator. The polymer was characterized by SEM and FTIR. Adsorption binding isotherms were evaluated using Langmuir and Freundlich models, showing high adsorption capacity for both inorganic and organic mercury species. The polymer was employed to sequentially determine inorganic mercury and methylmercury, using a solid phase extraction (SPE) scheme. Cross reactivity of several ions, as well as matrix effects from a high saline matrix like seawater was irrelevant as the retained fractions mostly eluted during the washing step. The procedure was first validated by analyzing a certified reference material (BCR 464) and finally applied to commercial fish samples. The speciation proposed procedure is cheap, fast, and easy to use and minimizes reagents waste.
RESUMO
Fischer carbene complexes 1-7 are not ionized under standard electrospray ionization (ESI) conditions. We report here that unsaturated chromium and tungsten (Fischer) carbene complexes can be ionized in an electrospray ion source in the presence of electron-donor compounds such as hydroquinone (HQ) or tetrathiafulvalene (TTF). The addition of these compounds, which seem to act as electron transfer agents, permits the recording and study of their ESI mass spectra in the negative mode of detection. Both chromium and tungsten(0) carbene complexes undergo in the first fragmentation stage a double simultaneous decarbonylation process.
Assuntos
Elétrons , Metano/análogos & derivados , Metano/análise , Espectrometria de Massas por Ionização por Electrospray/métodos , Cromo/química , Compostos Heterocíclicos/química , Hidrocarbonetos , Hidroquinonas/química , Íons/química , Nitrilas/química , Cloreto de Tolônio/química , Tungstênio/químicaRESUMO
The use of group 6 metal-carbene complexes in inter- and intramolecular carbene transfer reactions has been studied. Thus, pentacarbonyl[(aryl)(methoxy)carbene]chromium(0) and tungsten complexes, 10, efficiently dimerize at room temperature in the presence of diverse Pd(0) and Pd(II)/Et(3)N catalysts. The effect of additives (PPh(3), AsPh(3), or SbPh(3)) on the nature and the isomeric ratio of the reaction products is negligible. The nature of the reaction products is more catalyst-dependent for metal carbenes 12 bearing alkyl groups attached to the carbene carbon. In these cases, either carbene ligand dimerization or beta-hydrogen elimination reactions are observed, depending on the catalyst. The carbene ligand dimerization reaction can be used to prepare conjugated polyenes, including those having metal moieties at both ends of the polyene system, as well as enediyne derivatives. The intramolecular carbene ligand dimerization of chromium bis-carbene complexes 28 and 30 allows the preparation of mono- and bicyclic derivatives, with ring sizes from six to nine members. For bis-carbene derivatives the beta-hydrogen elimination reaction is inhibited, provided that both metal centers are tethered by an o-xylylene group. Other alkyl complexes 32 form new mononuclear carbene complexes 37 or decompose to complex reaction mixtures. The results obtained in these reactions may be explained by transmetalation from Cr(0) to Pd(0) and the intermediacy of Pd-carbene complexes. Aminocarbene-chromium(0) complexes 15, need harsher reaction conditions to transfer the carbene ligand, and this transfer occurs only in the presence of deactivated olefins. The corresponding insertion/hydrolysis products 48 resulted in these cases. A catalytic cycle involving transmetalation from a chromacyclobutane to a palladacyclobutane is proposed to explain these results.
RESUMO
The photochemical reaction of alkoxychromium(0)carbene complexes and ferrocene mono- and disubstituted imines formed 2-azetidinones having one or two ferrocene moieties in good yields. Yields decrease when the carbene moiety bears an aminoferrocene moiety attached to the carbene carbon, while complex 9 having the ferrocene directly bonded to the carbene carbon was totally inert in these reactions. Access to beta-lactams with the ferrocene tethered to the C3 position through a methylene group was gained using the lithium enolate derived from ethyl 3-ferrocenylpropanoate. The reaction of this enolate produced two unexpected processes. Thus, 2-azetidinone 15 having an hydroxyl group at the C3 position was obtained together with the expected beta-lactam 14, by reaction of the lithium enolate of ethyl 3-ferrocenylpropenoate and imine 1. Additionally, unsaturated amide 17 was obtained by base-promoted Hoffmann-like breakage of the beta-lactam ring formed in the reaction of the same enolate and imine 2. Oxidation of the anion at the C3 of the 2-azetidinone ring on compound 14, as well as the sterically driven ring-breakage of the C3 anion derived from the nonisolated 2-azetidinone 18, should be responsible for this behavior.