Luis F. Giraldo

Poly(methyl acrylate) plus Mesoporous Silica Nanohybrids: Mechanical and Thermophysical Properties

Abstract A mesoporous silica MCM-48 is used as a reinforcement agent for poly(methyl acrylate) (PMA). Methyl acrylate is introduced into the mesoporous silica that has an interconnected porous structure, allowing monomer diffusion into the pores before the polymerization reaction. In order to improve the silica plus polymer adhesion and to decrease the silica agglomeration, the silanol groups of the silica are functionalized with methyl groups without decreasing significantly the pore size. The silica is characterized by nitrogen adsorption, scanning electronic microscopy (SEM) and infrared (IR) spectroscopy. The nanohybrids so obtained are analyzed by tensile testing, thermogravimetry (TGA), differential scanning calorimetry (DSC) and dynamical mechanical analysis (DMA). The highest improvement of mechanical and thermophysical properties is achieved for nanohybrids containing 5 wt. % mesoporous silica. At 10 % silica, agglomeration of the filler takes place and the dispersed phase is less effective in reinforcing the polymer matrix.

Ionic liquids intercalated in montmorillonite as the sorptive phase for the extraction of low-polarity organic compounds from water by rotating-disk sorptive extraction

Montmorillonite (MMT) clays were modified by the intercalation into their galleries of ionic liquids (IL) based on imidazolium quaternary ammonium salts. This new eco-materials exhibited good features for use as a sorptive phase in the extraction of low-polarity analytes from aqueous samples. Spectroscopic analyses of the modified clays were conducted and revealed an increase in the basal spacing and a shifting of the reflection plane towards lower values as a consequence of the effective intercalation of organic cations into the MMT structure. The novel sorbent developed herein was assayed as the sorptive phase in rotating-disk sorptive extraction (RDSE), using polychlorinated biphenyls (PCBs), representative of low-polarity pollutants, as model analytes. The final determination was made by gas chromatography with electron capture detection. Among the synthetized sorptive phases, the selected system for analytical purposes consisted of MMT modified with the 1-hexadecyl-3-methylimidazolium bromide (HDMIM-Br) IL. Satisfactory analytical features were achieved using a sample volume of 5xa0mL: the relative recoveries from a wastewater sample were higher than 80%, the detection limits were between 3xa0ngxa0L-1 and 43xa0ngxa0L-1, the precision (within-run precision) expressed as the relative standard deviation ranged from 2% to 24%, and the enrichment factors ranged between 18 and 28. Using RDSE, the extraction efficiency achieved for the selected MMT-HDMIM-Br phase was compared with other commercial solid phases/supports, such as polypropylene, polypropylene with 1-octanol (as a supported liquid membrane), octadecyl (C18) and octyl (C8), and showed the highest response for all the studied analytes. Under the optimized extraction conditions, this new device was applied in the analysis of the influent of a wastewater treatment plant in Santiago (Chile), demonstrating its applicability through the good recoveries and precision achieved with real samples.

Formation of functionalized nanoclusters by solvent evaporation and their effect on the physicochemical properties of dental composite resins

OBJECTIVEnThe aim of this work was to study the effect of silica nanoclusters (SiNC), obtained by a solvent evaporation method and functionalized by 3-methacryloxypropyltrimethoxysilane (MPS) and MPS+octyltrimethoxysilane (OTMS) (50/50wt/wt), on the rheological, mechanical and sorption properties of urethane dimethylacrylate (UDMA)/triethylenglycol dimethacrylate (TEGDMA) (80/20wt/wt) resins blend.nnnMETHODSnSilica nanoparticles (SiNP) were silanized with MPS or MPS+OTMS (50/50wt/wt) and incorporated in an UDMA-isopropanol mix to produce functionalized silica nanoclusters after evaporating the isopropanol. The effect of functionalized SiNC on resins rheological properties was determined by large and small deformation tests. Mechanical, thermal, sorption and solubility properties were evaluated for composite materials.nnnRESULTSnThe UDMA/TEGDMA (80/20wt/wt) resins blend with added SiNC (ca. 350nm) and functionalized with MPS showed a Newtonian flow behavior associated to their spheroidal shape, whereas the resins blend with nanoclusters silanized with MPS+OTMS (50/50wt/wt) (ca. 400nm) showed a shear-thinning behavior due to nanoclusters irregular shape. Composite materials prepared with bare silica nanoclusters showed lower compressive strength than functionalized silica nanoclusters. MPS functionalized nanoclusters showed better mechanical properties but higher water sorption than functionalized nanoclusters with both silane coupling agents, MPS and OTMS.nnnSIGNIFICANCEnThe solvent evaporation method applied to functionalized nanoparticles showed to be an alternative way to the sinterization method for producing nanoclusters, which improved some dental composite mechanical properties and reduced water sorption. The shape of functionalized silica nanoclusters showed to have influence on the rheological properties of SiNC resin suspensions and the mechanical and sorption properties of light cured composites.

Synthesis of multiwall carbon nanotubes by using mesoporous aluminosilicates

Abstract Multiwall carbon nanotubes (MWCNTs) have been synthesized by catalytic chemical vapor deposition (CCVD) of ethylene on several mesoporous aluminosilicates impregnated with iron. The aluminosilicates were synthesized by sol-gel method optimizing the Si/Al ratios from 6 to 80. The catalysts are characterized by nitrogen adsorption, X-ray diffraction, 27Al NMR, thermogravimetric analysis (TGA) and infrared. The MWCNTs are characterized by TGA and transmission and scanning electron microscope. The aluminum is incorporated in a tetrahedral way into the mesoporous structure, given place to Bronsted acidic sites which are corroborated by FTIR using pyridine as probe molecule. The presence of aluminum reduces the quantity of amorphous carbon produced in the synthesis of carbon nanotubes which does not happen for mesoporous silica impregnated only with iron. It was observed a decrease in thermal stability of MWCNTs due to the presence of more metal particles which help to their earlier oxidation process.

Síntesis y funcionalización de nanopartículas de sílica conmorfología esférica

Nanoparticulas de silica de dos tamanos diferentes con geometria esferica se han sintetizado por el metodo Stober en medio basico. Posteriormente las nanoparticulas han sido funcionalizadas con 3-aminopropiltrimetoxisilano (AMPS) para su posterior uso como agente de refuerzo para poliamidas por las posibles interacciones entre la matriz polimerica y los grupos amino generados en la superficie de las particulas. Se determino efectividad de la funcionalizacion e las nanoparticulas por 29Si NMR, FTIR y TGA, su tamano y morfologia por SEM y TEM, su estabilidad por TGA.

Chitosan-acrylic polymeric nanoparticles with dynamic covalent bonds. Synthesis and stimuli behavior

Drug delivery represents one of the most important research fields within the pharmaceutical industry. Different strategies are reported every day in a dynamic search for carriers with the ability to transport drugs across the body, avoiding or decreasing toxic issues and improving therapeutic activity. One of the most interesting strategies currently under research is the development of drug delivery systems sensitive to different stimuli, due to the high potential attributed to the selective delivery of the payload. In this work, a stimuli-sensitive nanocarrier was built with a bifunctional acrylic polymer, linked by imine and disulfide bonds to thiolate chitosan, the latter being a biopolymer widely known in the field of tissue engineering and drug delivery by its biodegradability and biocompatibility. These polymer nanoparticles were exposed to different changes in pH and redox potential, which are environments commonly found inside cancer cells. The results proof the ability of the nanoparticles to keep the original structure when either changes in pH or redox potential were applied individually. However, when both stimuli were applied simultaneously, a disassembly of the nanoparticles was evident. These special characteristics make these nanoparticles suitable nanocarriers with potential for the selective delivery of anticancer drugs.