Synthesis and structural characterization of poly(dicyclopentadiene) gels obtained with a novel ditungsten versus conventional W and Ru mononuclear catalysts

Poly(dicyclopentadiene) (PDCPD) gels were prepared via ring opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD), which is known to provide highly crosslinked insoluble polymers. Two catalytic systems were employed, both based on W compounds. The first one was based on the ditungsten complex Na[W2(μ-Cl)3 Cl4(THF)2] (THF)3 ({W3W}6+, a'2e'4) and the second one on commercially available WCl6. Both catalysts require activation by small amounts of phenylacetylene (PA). Drygels were characterized with TGA, FTIR-ATR, FT-Raman and solid-state NMR, and were compared with PDCPD aerogels synthesized using the well-established first and second generation Ru-based Grubbs’ catalysts (Ru-I and Ru-II). Emphasis is given on the determination of the cis/trans ratio of the polymeric chain. Data confirmed that Ru-based catalysts favor the trans-configuration, while W-based catalysts favor the cis-configuration, in accord with the stereoselectivity that has been observed with those catalytic systems in other ROMP reactions of substrates that yield soluble polymers. Most importantly, it is also shown that the configuration of the polymeric chain plays a key role in the swelling behavior of those PDCPD dry-gels in toluene. High-cis PDCPD gels obtained from the ditungsten catalytic system increased their volume by more than 100 times, while gels obtained with the other catalytic systems swelled to a much lesser extent (WCl6/PA, Ru-II), or did not swell at all (Ru-I). It is evident that swelling strongly depends on the configuration of the polymeric chain and increases together with the content of the cis configuration. Therefore, the ditungsten catalytic system shows unique advantages in terms of stereochemistry and properties of PDCPD gels over the mononuclear W- and Ru-based catalytic systems

Magnetically Driven Floating Foams for the Removal of Oil Contaminants from Water

In this study, we present a novel composite material based on commercially available polyurethane foams functionalized with colloidal superparamagnetic iron oxide nanoparticles and submicrometer polytetrafluoroethylene particles, which can efficiently separate oil from water. Untreated foam surfaces are inherently hydrophobic and oleophobic, but they can be rendered water-repellent and oil-absorbing by a solvent-free, electrostatic polytetrafluoroethylene particle deposition technique. It was found that combined functionalization of the polytetrafluoroethylene-treated foam surfaces with colloidal iron oxide nanoparticles significantly increases the speed of oil absorption. Detailed microscopic and wettability studies reveal that the combined effects of the surface morphology and of the chemistry of the functionalized foams greatly affect the oil-absorption dynamics. In particular, nanoparticle capping molecules are found to play a major role in this mechanism. In addition to the water-repellent and oil-absorbing capabilities, the functionalized foams exhibit also magnetic responsivity. Finally, due to their light weight, they float easily on water. Hence, by simply moving them around oil-polluted waters using a magnet, they can absorb the floating oil from the polluted regions, thereby purifying the water underneath. This low-cost process can easily be scaled up to clean large-area oil spills in wate

Formation and magnetic manipulation of periodically aligned microchains in thin plastic membranes

We demonstrate the fabrication of polymeric membranes that incorporate a few layers of periodically aligned magnetic microchains formed upon the application of variable magnetic fields. A homogeneous solution containing an elastomeric polymer and a small amount of colloidal magnetic nanoparticles is spin coated on glass slides, thereby forming thin magnetic membranes of ca. 10 μm thickness. Subsequent application of a homogeneous magnetic field results in the orientation of the magnetic clusters and their further motion into the matrix along the field lines forming layers of aligned chains. The study of the kinetics of alignment demonstrates that the chains are formed in the first hour of exposure to the magnetic field. Above all, a detailed microscopy study reveals that the dimensions and the periodicity of the microchains are effectively controlled by the intensity of the magnetic field, in good agreement with the theoretical simulations. This ability to form and manipulate the size and the distribution of chains into the polymeric matrix gives the opportunity to develop multifunctional composite materials ready to be used in various applications such as electromagnetic shielding, or multifunctional magnetic membranes etc

Magnetic Field Induced Formation of Magnetic Wires into Thin Elastic Membranes with Controlled Properties

We present the fabrication of magnetic elastomeric membranes consisting of aligned superparamagnetic microwires embedded in a polymeric matrix. The wires are formed by the magnetic assembly of colloidal iron oxide nanoparticles (NPs) dispersed in the prepolymer matrix, during the curing of the polymer and the solvent evaporation. The appropriate combination of the NPs quantity and of the viscosity of the matrix results in the formation of thin membranes of about 10mm, containing few layers of aligned wires which after the polymer curing are blocked in fixed position into the matrix. The orientation and the dimensions of the magnetic wires depend on the direction and intensity of the external MF respectively

Poly(urethane-norbornene) Aerogels via Ring Opening Metathesis Polymerization of Dendritic Urethane-Norbornene Monomers: Structure-Property Relationships as a Function of an Aliphatic Versus an Aromatic Core and the Number of Peripheral Norbornene Moieties

We report the synthesis and characterization of synthetic polymer aerogels based on dendritic-type urethane-norbornene monomers. The core of those monomers is based either on an aromatic/rigid (TIPM/Desmodur RE), or an aliphatic/flexible (Desmodur N3300) triisocyanate. The terminal norbornene groups (three at the tip of each of the three branches) were polymerized via ROMP using the inexpensive 1st generation Grubbs catalyst. The polymerization/gelation conditions were optimized by varying the amount of the catalyst. The resulting wet-gels were dried either from pentane under ambient pressure at 50 oC, or from t-butanol via freeze-drying, or by using supercritical fluid (SCF) CO2. Monomers were characterized with high resolution mass spectrometry (HRMS), 1H- and solid-state 13C-NMR. Aerogels were characterized with ATR-FTIR and solid-state 13C-NMR. The porous network was probed with N2-sorption and SEM. The thermal stability of monomers and aerogels was studied with TGA, which also provides evidence for the number of norbornene groups that reacted via ROMP. At low densities (<0.1 g cm-3) all aerogels were highly porous (porosity > 90%), mostly macroporous materials; aerogels based on the aliphatic/flexible core were fragile, whereas aerogels containing the aromatic/rigid core were plastic, and at even lower densities (0.03 g cm-3) foamy. At higher densities (0.2–0.7 g cm-3) all materials were stiff, strong, and hard. At low monomer concentrations all aerogels consisted of discrete primary particles that formed spherical secondary aggregates. At higher monomer concentrations the structure consisted of fused particles with the size of the previous secondary aggregates, due to the low solubility of the developing polymer, which phase-separated and formed a primary particle network. Same-size fused aggregates were observed for both aliphatic and aromatic triisocyanate-derived aerogels, leading to the conclusion that it is not the aliphatic or aromatic core that determines phase separation, but rather the solubility of the polymeric backbone (polynorbornene) that is in both cases the same. The material properties were compared to those of analogous aerogels bearing only one norbornene moiety at the tip of each branch deriving from the same cores

Asymmetric Assembling of Iron Oxide Nanocubes for Improving Magnetic Hyperthermia Performance

Magnetic hyperthermia (MH) based on magnetic nanoparticles (MNPs) is a promising adjuvant therapy for cancer treatment. Particle clustering leading to complex magnetic interactions affects the heat generated by MNPs during MH. The heat efficiencies, theoretically predicted, are still poorly understood because of a lack of control of the fabrication of such clusters with defined geometries and thus their functionality. This study aims to correlate the heating efficiency under MH of individually coated iron oxide nanocubes (IONCs) versus soft colloidal nanoclusters made of small groupings of nanocubes arranged in different geometries. The controlled clustering of alkyl-stabilized IONCs is achieved here during the water transfer procedure by tuning the fraction of the amphiphilic copolymer, poly(styrene-co-maleic anhydride) cumene-terminated, to the nanoparticle surface. It is found that increasing the polymer-to-nanoparticle surface ratio leads to the formation of increasingly large nanoclusters with defined geometries. When compared to the individual nanocubes, we show here that controlled grouping of nanoparticles - so-called "dimers" and "trimers" composed of two and three nanocubes, respectively - increases specific absorption rate (SAR) values, while conversely, forming centrosymmetric clusters having more than four nanocubes leads to lower SAR values. Magnetization measurements and Monte Carlo-based simulations support the observed SAR trend and reveal the importance of the dipolar interaction effect and its dependence on the details of the particle arrangements within the different clusters

Investigation of the electro-spinnability of alginate solutions containing gold precursor HAuCl4

Alginate nanofibers with an average diameter of 75 nm have been prepared by the electrospinning process. In addition, the spinnability of the solutions in the presence of the gold precursor HAuCl4 was investigated. At low concentrations of HAuCl4 well-formed nanofibers were produced, whereas as its concentration increases the nanofibrous mats present an increased number of bead-like defects. Herein, the in situ preparation of gold nanoparticles (Au NPs) is discussed since sodium alginate (SA) acts as the reducing agent and a mechanism is proposed in order to explain the bead-effect as well as the surface morphology of the alginate fibers decorated with Au NPs

Tailoring the morphology of poly(ethylene oxide)/silver triflate blends: from crystalline to self-assembled nanofibrillar structures.

Interaction of polyethylene oxide (PEO) with transition metal triflates is a newly emerging research area due to its numerous application fields, such as thin-film power conversion devices and sensors. In the present study, we demonstrate, for the first time, that PEO can solvate silver triflate organic salts in large quantities when formic acid is used as a common solvent for both. Nanocomposites with unique structural and electrical properties are fabricated by simply drop casting formic acid solutions of PEO and silver triflate salts. We present a detailed experimental study on the characterization of morphological and electrical properties of PEO–silver triflate nanocomposite films as a function of silver triflate concentration and discuss their potential applications as humidity sensors. In particular, by increasing the concentration of the salt in the initial solution the morphological features of the formed nanocomposites can be varied from well defined microcrystals to amorphous nanofibers. Of special interest are the nanocomposite films fabricated from a 1:1 (PEO-unit:Ag+) molar ratio, since they consist of self-assembled nanofibrillar structures, which exhibit good electrical conductivity as well as highly repeatable sensitivity towards humidity