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A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes

Norbornene can be polymerized by a variety of mechanisms, including insertion polymerization whereby the double bond is polymerized and the bicyclic ...

Université de Sherbrooke

Linear copolymers of ethylene and acrylic acid (PEAA) were prepared by catalytic polymerization of ethylene and tert-butyl acrylate followed by hydrolysis of the ester groups. The copolymers contained COOH groups inserted into the crystalline unit cell with formation of intramolecular hydrogen-bonds, as established on the basis of differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) studies. A solvent-exchange protocol, with no added surfactant, converted a solution in tetrahydrofuran of a PEAA sample containing 12 mol % of acrylic acid (AA) into a colloidally stable aqueous suspension of nanoparticles. Transmission electron microscopy (TEM), dynamic light scattering (DLS), and high sensitivity differential scanning calorimetry (HS-DSC) were used to characterize the nanoparticles. They are single crystals of elongated shape with a polar radius of 49 nm (σ = 15 nm) and an equatorial radius of 9 nm (σ = 3 nm) stabilized in aqueous media via carboxylate groups located preferentially on the particle/water interface. The PEAA (AA: 12 mol %) nanoparticles dispersed in aqueous media exhibited a remarkable reversible thermoresponsive behavior upon heating/cooling from 25 to 80 °C.

Amphiphilic polyethylenes leading to surfactant-free thermoresponsive nanoparticles.

A ruthenium phosphane aryl sulfonate was found to be an efficient catalyst for the polymerization of ethene. Surprisingly, the resulting polyethylene is crosslinked.

A ruthenium catalyst yielding crosslinked polyethylene.

Parallel-artificial membrane permeation assay (PAMPA) is widely used to rapidly measure drug permeability across a biological membrane. We have prepared model PAMPAs by supporting a lipid bilayer on a hydrated polymeric cushion adsorbed at the surface of a nanoporous alumina filter. In contrast to conventional PAMPAs, the natural fluidity of the bilayer is expected to be conserved in these model PAMPAs. The assembly was characterized by contact angle measurement and atomic force microscopy (AFM) and the supported membranes were mounted in a Franz cell setup to assess the permeability of acetaminophen and famotidine. The permeability profiles for the model PAMPA were compared to those of conventional PAMPA.

Supported bilayer on a nanopatterned membrane as model PAMPA membranes.

Palladium phosphanesulfonate [R(2)P(C(6)H(4)-o-SO(3))PdMeL] catalysts permit the copolymerization of an exceptional large number of functional olefins with ethylene. However, these catalysts usually have reduced activity. We here have conducted a systematic study on the influence of the phosphane substituent, R, on activity and molecular weight. Phosphanes with strong σ-donating character are shown to lead to the most active catalysts. Thus, the catalyst based on phosphane bis-tert-butyl-phosphanyl-benzenesulfonic acid (R=tBu) exhibits unprecedented high activity, rapidly polymerizing ethylene at room temperature to yield a linear polymer of high molecular weight (M(w)=116,000 g mol(-1)). The influence of the R group on the catalyst ability to incorporate methyl acrylate is also investigated.

Structure-activity relationship of palladium phosphanesulfonates: toward highly active palladium-based polymerization catalysts.

Copolymers of 2-ethylhexyl acrylate (EHA) and cholesteryloxycarbonyl-2-hydroxymethacrylate (CEM) were prepared by reversible addition-fragmentation chain-transfer (RAFT) polymerization. Supramolecular complexes of these copolymers with carbon nanotubes (CNTs) were soluble in THF, toluene, and isooctane. The colloidal solutions remained stable for months without aggregation. The rationale for the choice of CEM was based on the high adsorption energy of cholesterol on the CNT surface, as computed by DFT calculations. Adsorption isotherms were experimentally measured for copolymers of various architectures (statistical, diblock, and star copolymers), thereby demonstrating that 2-5 cholesterol groups were adsorbed per polymer chain. Once the supramolecular complex had dried, the CNTs could be easily resolubilized in isooctane without the need for high-power sonication and in the absence of added polymer. Analysis by atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) indicated that the CNTs were devoid of bundles. The supramolecular complexes could also be employed in an inverse emulsion polymerization of 2-hydroxyethylmethacrylate (HEMA) in isooctane and dodecane, thereby leading to the formation of a continuous polymeric sheath around the CNTs. Thus, this technique leads to the formation of very stable dispersions in non-polar organic solvents, without altering the fundamental properties of the CNTs.

Supramolecular complexes of multivalent cholesterol-containing polymers to solubilize carbon nanotubes in apolar organic solvents.

A facile method is proposed to assemble graphene oxide (GO) on the surface of a TiO2 nanobelt followed by an in situ photocatalytic reduction to form reduced graphene oxide (rGO)/TiO2 nanobelt surface heterostructures. The special colloidal properties of GO and TiO2 nanobelt are exploited as well as the photocatalytic properties of TiO2 . Using water-ethanol solvent mixtures, GO nanosheets are tightly wrapped around the surface of the TiO2 nanobelts through an aggregation process and are then reduced in situ under UV-light irradiation to form rGO/TiO2 nanobelt surface heterostructures. The heterostructures enhance the separation of the photoinduced carriers, which results in a higher photocurrent due to the special electronic characteristics of rGO. Compared to TiO2 nanobelts, the rGO/TiO2 nanobelt surface heterostructures possess higher photocatalytic activity for the degradation of methyl orange and for the production of hydrogen from water, as well as excellent recyclability, with no loss of activity over five cycles.

Enhanced photocatalytic property of reduced graphene oxide/TiO2 nanobelt surface heterostructures constructed by an in situ photochemical reduction method.

TiO2 semiconducting nanoparticles are known to be photocatalysts of moderate activity due to their high band-gap and high rate of electron-hole recombination. The formation of a shell of carbon around the core of TiO2, i.e., the formation of TiO2@C nanoparticles, is believed to partly alleviate these problems. It is usually achieved by a hydrothermal treatment in a presence of a sugar derivative. We present here a novel method for the formation of highly uniform C shell around TiO2 nanoparticles. For this purpose, TiO2 nanoparticles were dispersed in water using an oligomeric dispersant prepared by Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization. Then the nanoparticles were engaged into an emulsion polymerization of acrylonitrile, resulting in the formation of a shell of polyacrylonitrile (PAN) around each TiO2 nanoparticles. Upon pyrolysis, the PAN was transformed into carbon, resulting in the formation of TiO2@C nanoparticles. The structure of the resulting particles was elucidated by X-Ray diffraction, FTIR, UV-VIS and Raman spectroscopy as well as TEM microscopy. Preliminary results about the use of the TiO2@C particles as photocatalysts for the splitting of water are presented. They indicate that the presence of the C shell is responsible for a significant enhancement of the photocurrent.

TiO2@C core-shell nanoparticles formed by polymeric nano-encapsulation.

Nanocomposites composed of TiO2 and carbon materials (C) are widely popular photocatalysts because they combine the advantages of TiO2 (good UV photocatalytic activity, low cost, and stability) to the enhanced charge carrier separation and lower charge transfer resistance brought by carbon. However, the presence of carbon can also be detrimental to the photocatalytic performance as it can block the passage of light and prevent the reactant from accessing the TiO2 surface. Here using a novel interfacial in situ polymer encapsulation-graphitization method, where a glucose-containing polymer was grown directly on the surface of the TiO2, we have prepared uniform TiO2@C core-shell structures. The thickness of the carbon shell can be precisely and easily tuned between 0.5 and 8 nm by simply programming the polymer growth on TiO2. The resulting core@shell TiO2@C nanostructures are not black and they possess the highest activity for the photodegradation of organic compounds when the carbon shell thickness is 1-2 nm, corresponding to ∼3-5 graphene layers. Photoluminescence and photocurrent generation tests further confirm the crucial contribution of the carbon shell on charge carrier separation and transport. This in situ polymeric encapsulation approach allows for the careful tuning of the thickness of graphite-like carbon, and it potentially constitutes a general and efficient route to prepare other oxide@C catalysts, which can therefore largely expand the applications of nanomaterials in catalysis.

TiO2@Carbon Photocatalysts: The Effect of Carbon Thickness on Catalysis.

Recently, surface plasmon resonance (SPR) effects have been widely used to construct photocatalysts which are active in the visible spectral region. Such plasmonic photocatalysts usually comprise a semiconductor material transparent in the visible range (such as TiO2) and plasmonic nano-objects (e.g., Au nanoparticles (Au NPs)). Specific SPRs, though, only partially cover the visible spectrum and feature weak light absorption. Here, we explore the unique role played by whispering gallery mode (WGM) resonances in the expression of the photocatalytic activity of plasmonic photocatalysts. Using numerical simulations, we demonstrate that, by solely exploiting a proper geometrical arrangement and WGM resonances in a TiO2 sphere, the plasmonic absorption can be extended over the entire visible range and can be increased by more than 40 times. Furthermore, the local electric field at the Au-TiO2 interface is also considerably enhanced. These results are experimentally corroborated, by means of absorption spectroscopy and Raman measurements. Accordingly, such WGM-assisted plasmonic photocatalysts, when employed in water splitting experiments, exhibit enhanced activity in the visible range. Our findings show a promising and straightforward way to design full solar spectrum photocatalysts.

Engineering the Absorption and Field Enhancement Properties of Au-TiO2 Nanohybrids via Whispering Gallery Mode Resonances for Photocatalytic Water Splitting.

Bacillus thuringiensis (B. t.) based formulations have been widely used to control lepidopteran pests in agriculture and forestry. One of their weaknesses is their short residual activity when sprayed in the field. Using Pickering emulsions, mixtures of spores and crystals from three B. t. serovars were successfully encapsulated in colloïdosomal microparticles (50 μm) using innocuous chemicals (acrylic particles, sunflower oil, iron oxide nanoparticles, ethanol and water). A pH trigger mechanism was incorporated within the particles so that B. t. release occurred only at pH > 8.5 which corresponds to the midgut pH of the target pests. Laboratory assays performed on Trichoplusia ni (T. ni) larvae demonstrated that the microencapsulation process did not impair B. t. bioactivity. The best formulations were field-tested on three key lepidopteran pests that attack Brassica crops, i.e., the imported cabbageworm, the cabbage looper and the diamondback moth. After 12 days, the mean number of larvae was significantly lower in microencapsulated formulations than in a commercial B. t. formulation, and the effect of microencapsulated formulations was comparable to a chemical pesticide (lambda-cyhalothrin). Therefore, colloïdosomal microcapsule formulations successfully extend the bioactivity of B. t. for the management of lepidopteran pests of Brassica crops.

Controlled-release of Bacillus thurigiensis formulations encapsulated in light-resistant colloidosomal microcapsules for the management of lepidopteran pests of Brassica crops.

We report the two-step synthesis of a core@shell nanohybrid material for visible-to-near-infrared (NIR) photocatalysis. The core is constituted of NaGdF4:Er(3+), Yb(3+) upconverting nanoparticles (UCNPs). A bismuth ferrite (BFO) shell is assembled around the UCNPs via a hydrothermal process. The photocatalytic degradation assays of organic compounds of methylene orange and 4-chlorophenol reveal that core@shell nanostructures possess remarkably enhanced reaction activity under visible and NIR irradiation, compared to the BFO powder alone and the BFO-UCNP mixture. Photo-charge scavenger tests and fluorescent assays indicate that hydroxyl radicals play a pivotal role in the photodegradation mechanism. The enhanced photoactivity of the core@shell structure is attributed to the NIR radiation which is converted into visible light by UCNPs, and which is then captured by BFO via a nonradiative luminescence resonance energy transfer process. Therefore, this core@shell architecture optimizes solar energy use by efficiently harvesting visible and NIR photons.

Jerome P. Claverie

Department of Chemistry

Université de Sherbrooke

A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes

Jerome P. Claverie

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}Department of Chemistry

Université de Sherbrooke

A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes

Department of Chemistry