Effect of pH and Monomer Dosing Rate in the Anionic Polymerization of Ethyl Cyanoacrylate in Semicontinuous Operation

Nanoparticles of poly(ethyl cyanoacrylate) with more than 10% solids content were prepared by semicontinuous heterophase polymerization at monomer-starved conditions varying the initial pH in the interval of 1–1.75 and at two monomer dosing rates. Measurements by scanning-transmission electron microscopy allowed us to identify an inverse dependence of particle size on pH. Furthermore, all the polymerizations conducted at the slower monomer dosing rate rendered two particle populations, with the larger one formed from the aggregation of a fraction of the smaller particles. It was believed that the so slow addition of the monomer caused the formation of very small but instable particles, thereby a fraction of which aggregated to reduce the total interface particles-aqueous phase, increasing the latex stability. An increase in the monomer dosing rate led to larger and more stable particles in such way that only one population of nanoparticles with around 40 nm in average diameter was obtained

Immobilization of Aspergillus niger lipase on chitosan-coated magnetic nanoparticles using two covalent-binding methods

Aspergillus niger lipase immobilization by covalent binding on chitosan-coated magnetic nanoparticles (CMNP), obtained by one-step co-precipitation, was studied. Hydroxyl and amino groups of support were activated using glycidol and glutaraldehyde, respectively. Fourier transform infrared spectrometry, high-resolution transmission electron microscopy and thermogravimetric analysis confirmed reaction of these coupling agents with the enzyme and achievement of a successful immobilization. The derivatives showed activities of 309.5 ± 2.0 and 266.2 ± 2.8 U (g support)(-1) for the CMNP treated with glutaraldehyde and with glycidol, respectively. Immobilization enhanced the enzyme stability against changes of pH and temperature, compared to free lipase. Furthermore, the kinetic parameters K m and V max were determined for the free and immobilized enzyme. K m value quantified for enzyme immobilized by means of glutaraldehyde was 1.7 times lowers than for free lipase. High storage stability during 50 days was observed in the immobilized derivatives. Finally, immobilized derivatives retained above 80% of their initial activity after 15 hydrolytic cycles. The immobilized enzyme can be applied in various biotechnological processes involving magnetic separation.Fil: Osuna, Yolanda. Universidad Autónoma de Coahuila; MéxicoFil: Sandoval, José. Universidad Autónoma de Coahuila; MéxicoFil: Saade, Hened. Centro de Investigación en Química Aplicada; MéxicoFil: López, Raúl G.. Centro de Investigación en Química Aplicada; MéxicoFil: Martinez, José L.. Universidad Autónoma de Coahuila; MéxicoFil: Colunga, Edith M.. Universidad Autónoma de Coahuila; MéxicoFil: de la Cruz, Gabriela. Universidad Autónoma de Coahuila; MéxicoFil: Segura, Elda P.. Universidad Autónoma de Coahuila; MéxicoFil: Arevalo, Fernando Javier. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Zon, María Alicia. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Fernandez, Hector. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Ilyina, Anna. Universidad Autónoma de Coahuila; Méxic

Nanocompuestos bio-basados de polimirceno/nanocristales de celulosa obtenidos por polimerización “in situ”

Se reporta la preparación de nanocompuestos elastoméricos 100 % bio-basados a partir de la polimerización de β-mirceno usando como carga nanocristales de celulosa, mediante un proceso “in situ”, es decir, llevar a cabo la polimerización en presencia de las nanocargas. La polimerización fue vía coordinación en solución usando un sistema catalítico base neodimio, NdV3/DIBAH/ Me2SiCl2 en relación molar 1/20/1 y variando la concentración de nanocristales de celulosa de 0.5, 1.5, 3 y 5 % en peso, los cuales fueron probados con y sin modificación superficial por plasma utilizando β-mirceno como modificante. Dicha modificación se demostró caracterizando los materiales mediante FTIR, XRD y TGA. Los nanocompuestos elastoméricos obtenidos se caracterizaron mediante GPC para la obtención de los pesos moleculares, así como por NMR para calcular el porcentaje de estructuras 1,4 (cis + trans) vs 3,4. A medida que se incrementó el porcentaje de la carga en las polimerizaciones se produjeron matrices poliméricas con mayores pesos moleculares y amplias distribuciones, pero el alto contenido de la microestructura cis-1,4 no se vio comprometido. La temperatura de transición vítrea tampoco fue significativamente modificada por las nanocargas, pero sí se observó un incremento en los módulos G’ y G’’ por la presencia de éstas. DOI: https://doi.org/10.54167/tch.v17i4.133

Chitosan-Coated Magnetic Nanoparticles Prepared in One Step by Reverse Microemulsion Precipitation

Chitosan-coated magnetic nanoparticles (CMNP) were obtained at 70 °C and 80 °C in a one-step method, which comprises precipitation in reverse microemulsion in the presence of low chitosan concentration in the aqueous phase. X-ray diffractometry showed that CMNP obtained at both temperatures contain a mixture of magnetite and maghemite nanoparticles with ≈4.5 nm in average diameter, determined by electron microscopy, which suggests that precipitation temperature does not affect the particle size. The chitosan coating on nanoparticles was inferred from Fourier transform infrared spectrometry measurements; furthermore, the carbon concentration in the nanoparticles allowed an estimation of chitosan content in CMNP of 6%–7%. CMNP exhibit a superparamagnetic behavior with relatively high final magnetization values (≈49–53 emu/g) at 20 kOe and room temperature, probably due to a higher magnetite content in the mixture of magnetic nanoparticles. In addition, a slight direct effect of precipitation temperature on magnetization was identified, which was ascribed to a possible higher degree of nanoparticles crystallinity as temperature at which they are obtained increases. Tested for Pb2+ removal from a Pb(NO3)2 aqueous solution, CMNP showed a recovery efficacy of 100%, which makes them attractive for using in heavy metals ion removal from waste water

Synthesis of Silver Nanoparticles by Precipitation in Bicontinuous Microemulsions

Silver nanoparticles precipitation was carried out at 70∘C in bicontinuous microemulsions stabilized with a mixture of surfactants sodium bis (2-ethylhexyl) sulfosuccinate/sodium dodecyl sulfate (2/1, w/w) containing an aqueous solution of 0.5 M silver nitrate and toluene as organic phase. Various concentrations of aqueous solution of sodium borohydride (precipitating agent) and their dosing times on microemulsions were studied. Regardless of dosing time, higher and medium concentrations of precipitating agent promoted the formation of worm-like nanostructures, while the lowest concentration allowed to obtain a mixture of isolated silver nanoparticles (mean diameter ≈3 nm) and worm-like nanostructures. Experimental yields much higher than those typical in precipitation of silver nanoparticles in reverse microemulsions were obtained. An explanation for formation of worm-like nanostructures based on the development of local zones inside the microemulsions channels with high particle concentrations was proposed

Precipitation of Zinc Oxide Nanoparticles in Bicontinuous Microemulsions

Zinc oxide nanoparticles were obtained directly, avoiding the calcination step, by precipitation at 70°C in bicontinuous microemulsions stabilized with a mixture of surfactants sodium bis (2-ethylhexyl) sulfosuccinate/sodium dodecyl sulfate (2/1, wt./wt.) containing 0.7 M zinc nitrate aqueous solution. Two concentrations of aqueous solution of precipitating agent sodium hydroxide were used under different dosing times on microemulsion. Characterization by X-ray diffraction and electron microscopy allowed us to identify particles with an acicular rod-like morphology and a hexagonal wurtzite crystal structure as small as 8.5 and 30 nm in average diameter and length, respectively. Productivities much higher than those typical in the preparation of zinc oxide nanoparticles via reverse microemulsions were obtained. Particle size was the same at the two studied sodium hydroxide concentrations, while it increases as dosing time of the precipitant agent increases. It is believed that the surfactant film on the microemulsion channels restricts the particle diameter growth

Chitosan-Coated Magnetic Nanoparticles Prepared in One-Step by Precipitation in a High-Aqueous Phase Content Reverse Microemulsion

Chitosan-coated magnetic nanoparticles (CMNP) were prepared in one-step by precipitation in a high-aqueous phase content reverse microemulsion in the presence of chitosan. The high-aqueous phase concentration led to productivities close to 0.49 g CMNP/100 g microemulsion; much higher than those characteristic of precipitation in reverse microemulsions for preparing magnetic nanoparticles. The obtained nanoparticles present a narrow particle size distribution with an average diameter of 4.5 nm; appearing to be formed of a single crystallite; furthermore they present superparamagnetism and high magnetization values; close to 49 emu/g. Characterization of CMNP suggests that chitosan is present as a non-homogeneous very thin layer; which explains the slight reduction in the magnetization value of CMNP in comparison with that of uncoated magnetic nanoparticles. The prepared nanoparticles show high heavy ion removal capability; as demonstrated by their use in the treatment of Pb2+ aqueous solutions; from which lead ions were completely removed within 10 min

One-Step Method for Preparation of Magnetic Nanoparticles Coated with Chitosan

Preparation of magnetic nanoparticles coated with chitosan in one step by the coprecipitation method in the presence of different chitosan concentrations is reported here. Obtaining of magnetic superparamagnetic nanoparticles was confirmed by X-ray diffraction and magnetic measurements. Scanning transmission electron microscopy allowed to identify spheroidal nanoparticles with around 10-11 nm in average diameter. Characterization of the products by Fourier transform infrared spectroscopy demonstrated that composite chitosan-magnetic nanoparticles were obtained. Chitosan content in obtained nanocomposites was estimated by thermogravimetric analysis. The nanocomposites were tested in Pb2+ removal from a PbCl2 aqueous solution, showing a removal efficacy up to 53.6%. This work provides a simple method for chitosan-coated nanoparticles obtaining, which could be useful for heavy metal ions removal from water

Chitosan-Coated Magnetic Nanoparticles with Low Chitosan Content Prepared in One-Step

Chitosan-coated magnetic nanoparticles (CMNP) were obtained at 50°C in a one-step method comprising coprecipitation in the presence of low chitosan content. CMNP showed high magnetization and superparamagnetism. They were composed of a core of 9.5 nm in average diameter and a very thin chitosan layer in accordance with electron microscopy measurements. The results from Fourier transform infrared spectrometry demonstrated that CMNP were obtained and those from thermogravimetric analysis allowed to determine that they were composed of 95 wt% of magnetic nanoparticles and 5 wt% of chitosan. 67% efficacy in the Pb+2 removal test indicated that only 60% of amino groups on CMNP surface bound to Pb, probably due to some degree of nanoparticle flocculation during the redispersion. The very low weight ratio chitosan to magnetic nanoparticles obtained in this study, 0.053, and the high yield of the precipitation reactions (≈97%) are noticeable