307 research outputs found

    Stannylated Vinylic Addition Polynorbornene: Probing a Reagent for Friendly Tin-Mediated Radical Processes

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    Producción CientíficaVinylic addition polynorbornenes (VA-PNB) with stannyl functional groups have been prepared and used in tin- mediated radical dehalogenation reactions. The aliphatic and robust scaffold of VA-PNB is well suited for a support in radical processes. VA-PNB-(CH2)nSnHBu2 can be used as a stoichiomet- ric reagent and VA-PNB-(CH2)nSnBu2Cl as a catalyst in the pres- ence of a hydride donor for the reduction of RBr. The mixture KF (aq.)/polymethylhydrosiloxane (PMHS) is the most convenient hydride source to generate VA-PNB-(CH2)nSnHBu2 in situ. Although quite popular in this context, boron hydrides, being a source of radicals themselves, are not adequate to correctly evaluate the performance of the anchored organotin group. VA- PNB-(CH2)4SnBu2Cl can be recycled and, even if it loses activity upon reuse, it is still useful after ten cycles. The stannylated VA- PNB can be separated from the products by simple filtration, and it leads to very low tin contamination (at least 250 times lower than that with use of conventional separation methods).MINECO-SGPI CTQ2013-48406-PMINECO-SGPI CTQ2016-80913-

    α-Diimine–Palladium Complexes Incorporated in Vinylic- Addition Polynorbornenes: Synthesis and Catalytic Activity

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    Producción Científicaα-Diimine polymeric ligands have been synthesized using the bicyclic norbornane structure, present in vinylic-addi- tion polynorbornene ( VA-PNB). The VA-PNB–diimine ligands have been prepared by functionalization of the copolymer ob- tained by Ni-catalyzed polymerization of norbornene and nor- bornenylcarbonate. Immobilized palladium complexes of the type VA-PNB–diimine–PdX2 have been prepared, and their cata- lytic activity has been tested. The trifluoroacetato complex (X =CF3COO) can be used as a recyclable precatalyst in the Suzuki reaction. It is the source of minute amounts of homogeneous palladium active species, which carry out the catalysis with high turnover numbers. The recovered polymeric complex can be reused several times with no significant loss of activity. The polymeric analogue to Brookhart's catalyst, VA-PNB–diimine– PdMeCl, can also polymerize ethylene, although it is less active than its monomeric counterparts.MINECO-SGPI, grant CTQ2013-48406-PMINECO-SGPI, grant CTQ2016-80913-PJunta de Castilla y León, grant VA302U1

    Template Route to Chemically Engineering Cavities at Nanoscale: A Case Study of Zn(OH)2 Template

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    A size-controlled Zn(OH)2 template is used as a case study to explain the chemical strategy that can be executed to chemically engineering various nanoscale cavities. Zn(OH)2 octahedron with 8 vertices and 14 edges is fabricated via a low temperature solution route. The size can be tuned from 1 to 30 μm by changing the reaction conditions. Two methods can be selected for the hollow process without loss of the original shape of Zn(OH)2 template. Ion-replacement reaction is suitable for fabrication of hollow sulfides based on the solubility difference between Zn(OH)2 and products. Controlled chemical deposition is utilized to coat an oxide layer on the surface of Zn(OH)2 template. The abundant hydroxyl groups on Zn(OH)2 afford strong coordination ability with cations and help to the coating of a shell layer. The rudimental Zn(OH)2 core is eliminated with ammonia solution. In addition, ZnO-based heterostructures possessing better chemical or physical properties can also be prepared via this unique templating process. Room-temperature photoluminescence spectra of the heterostructures and hollow structures are also shown to study their optical properties

    Inkjet printing of graphene

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    The inkjet printing of graphene is a cost-effective, and versatile deposition technique for both transparent and non-transparent conductive films. Printing graphene on paper is aimed at low-end, high-volume applications, i.e.; in electromagnetic shielding, photovoltaics or, e.g.; as a replacement for the metal in antennas of radio-frequency identification devices, thereby improving their recyclability and biocompatibility. Here, we present a comparison of two graphene inks, one prepared by the solubilization of expanded graphite in the presence of a surface active polymer, and the other by covalent graphene functionalization followed by redispersion in a solvent but without a surfactant. The non-oxidative functionalization of graphite in the form of a donor-type graphite intercalation compound was carried out by a Birch-type alkylation, where graphene can be viewed as a macrocarbanion. To increase the amount of functionalization we employed a graphite precursor with a high edge to bulk carbon ratio, thus, allowing us to achieve up to six weight percent of functional groups. The functionalized graphene can be readily dispersed at concentrations of up to 3 mg ml-1 in non-toxic organic solvents, and is colloidally stable for more than 2 months. The two inks are readily inkjet printable with good to satisfactory spreading. Analysis of the sheet resistance of the deposited films demonstrated that the inks based on expanded graphite outperform the functionalized graphene inks, possibly due to the significantly larger graphene sheet size in the former, which minimizes the number of sheet-to-sheet contacts along the conductive path. We found that the sheet resistance of printed large-area films decreased with an increase of the number of printed layers. Conductivity levels reached approximately 1-2 kΩ □-1 for 15 printing passes, which roughly equals a film thickness of 800 nm for expanded graphite based inks, and 2 MΩ □-1 for 15 printing passes of functionalized graphene, having a film thickness of 900 nm. Our results show that ink preparation and inkjet printing of graphene-based inks is simple and efficient, and therefore has a high potential to compete with other conductive ink formulations for large-area printing of conductive films

    Thermoreversible (Ionic-Liquid-Based) Aqueous Biphasic Systems

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    The ability to induce reversible phase transitions between homogeneous solutions and biphasic liquid-liquid systems, at pre-defined and suitable operating temperatures, is of crucial relevance in the design of separation processes. Ionic-liquid-based aqueous biphasic systems (IL-based ABS) have demonstrated superior performance as alternative extraction platforms, and their thermoreversible behaviour is here disclosed by the use of protic ILs. The applicability of the temperature-induced phase switching is further demonstrated with the complete extraction of two value-added proteins, achieved in a single-step. It is shown that these temperature-induced mono(bi)phasic systems are significantly more versatile than classical liquid-liquid systems which are constrained by their critical temperatures. IL-based ABS allow to work in a wide range of temperatures and compositions which can be tailored to fit the requirements of a given separation process
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