Márcio Nele

Preparation of high loading silica supported nickel catalyst: simultaneous analysis of the precipitation and aging steps

The precipitation and aging steps used for the preparation of high loading silica supported nickel catalysts were simultaneously analyzed with the aid of statistical design of experiments. Empirical models relating catalyst final properties and preparation variables were developed. It was found that the precipitation step determines the final catalyst nickel content, and that at low nickel concentrations high metallic area per gram of reduced nickel may be attained with the precipitated precursor without performing the aging step. When it is performed, the aging step has a strong influence on final catalyst properties, such as specific surface area, metallic area per gram of nickel and degree of reduction. Therefore, catalyst aging may be an effective method to control dispersion, reducibility and active phase accessibility. The importance of the aging step was shown to increase with the aging temperature, which is linked to the larger rates of silicate formation at high temperatures. A semi-empirical model was developed to describe the final catalyst specific surface area as a function of the rate of silicate formation. This model is able to describe changes of the catalyst surface area fairly well and allow the proper manipulation of preparation conditions in order to maximize the catalyst specific area, leading to maximum catalyst activities.

Computation of molecular weight distributions by polynomial approximation with complete adaptation procedures

The choice of appropriate reference functions is still the major drawback for collocation techniques to be used during the computation of molecular weight distributions (MWDs) in polymerization reactions and other problems constituted by systems of differential-difference equations. Complete adaptation procedures provide significant improvement of numerical approximations obtained, but convergence to the real solution is not assured and oscillatory numerical approximations may be obtained when the actual solution experiences large variations during time integration. An alternative method to compute the reference function in an adaptative manner, called here the integration of the reference function procedure, is presented. The technique is used to allow the computation of MWDs in two polymerization problems: the metallocene-based propene polymerization and the methyl methacrylate/butyl acrylate emulsion polymerization. The integration of the reference function procedure allowed the proper computation of broad, bimodal and fast changing distributions with polynomials of very low order (below 4), where other approximation techniques failed. The method may be easily implemented and does not require any pre-processing before implementation.

Molecular-Weight Multimodality of Multiple Flory Distributions

It is well-known that the final end-use properties of polymer resins depend on the shape of the molecular-weight distribution (MWD) very strongly. Particularly polymer resins with bimodal MWDs are required for certain special applications, as they may simultaneously present enhanced mechanical and flow properties. A theoretical framework for the characterization of bimodality (or multimodality) of MWDs of polymers produced through linear polymerizations at steady-state or quasi-steady-state conditions is developed and presented here. Conditions for the development of bimodality in generalized NS-Schulz-Flory distributions are characterized for different forms of presentation of the MWDs. It is shown that the bimodal character of the MWD depends on the particular form used to represent it, which can then be used to generate an index of bimodality of the MWD. The theoretical results are finally used to compute the index of bimodality of actual polymer materials obtained at plant site.

Renewable resources for biosurfactant production by yarrowia lipolytica

In this work, the production of a biosurfactant synthesized by Yarrowia lipolytica using different renewable resources as carbon source was investigated. Crude glycerol, a biodiesel co-product, and clarified cashew apple juice (CCAJ), an agroindustrial residue, were applied as feedstocks for the microbial surfactant synthesis. The microorganism was able to grow and produce biosurfactant on CCAJ and crude glycerol, achieving maximum emulsification indexes of 68.0% and 70.2% and maximum variations in surface tension of 18.0 mN.m-1and 22.0 mN.m-1, respectively. Different organic solvents (acetone, ethyl acetate and chloroform - methanol) were tested for biosurfactant extraction. Maximum biosurfactant recovery was obtained with chloroform - methanol (1:1), reaching 6.9 g.L-1for experiments using CCAJ and 7.9 g.L-1for media containing crude glycerol as carbon source.The results herein obtained indicate that CCAJ and the co-product of biodiesel production are appropriate raw materials for biosurfactant production by Y. lipolytica.

Preparation of high loading silica-supported nickel catalyst: analysis of the reduction step

The reduction step used for preparation of high loading silica-supported nickel (Ni/SiO 2) catalysts was analyzed with the help of statistical experimental design. Two catalyst precursors prepared by deposition–precipitation (DP) method and presenting significantly different metal–support interactions were studied. Empirical models were developed for the degree of reduction and for the metallic area of the Ni/SiO2 catalysts as functions of the reduction variables (final reduction temperature, heating rate, flow rate and hydrogen concentration of the reducing mixture) for each precursor. For the precursor with low nickel–support interaction, high degrees of reduction were attained regardless of the reducing conditions used; however, operation conditions exerted a significant influence upon the final catalyst metallic area. For the precursor with high nickel–support interaction, both the degree of reduction and the final catalyst metallic area were strongly affected by the reducing conditions. The reducing conditions were then optimized for both catalyst precursors in order to maximize the final catalyst metallic area. Simulation results were validated experimentally and indicated that optimum reducing conditions may depend significantly on the nature of the catalyst precursor. Finally, a mixed model was built by the linear combination of the two original models, allowing the successful optimization of the reducing conditions for a precursor with intermediate nickel–support interaction. These results suggest that reducing conditions may be tuned at plant site as a function of the metal–support interaction of catalyst precursors, with the aid of mathematical models built for model catalyst precursors.

Retrofitting of industrial olefin polymerization plants : Producing broad MWDs through multiobjective periodic operation

The drop-in of metallocene catalysts (MCs) in existing industrial polymerization plants is the current goal of most polymer producers. However, the narrow molecular weight distribution (MWD) of the polymers produced by MCs prevent them of moving into commodities market dominated by conventional Ziegler-Natta catalysts, where ease of processing is an essential property. Broader MWDs may be obtained through mixing of different MCs or blending of different resins, but resin-compatibility problems and complex undesirable catalyst interactions pose technological problems that have yet to be solved. For these reasons, modern olefin polymerization plants have to work with both catalysts to respond to market demands, resulting in costly operations of grade/catalyst change. In this article, we describe how periodic control of short residence-time reactors operating with an MC (Me 2 Si(2-Me-Benz[e]Ind) 2 ZrCl 2 /MAO) can lead to polymers with broad MWD and, consequently, to high processability.

Simultaneous encapsulation of magnetic nanoparticles and zinc phthalocyanine in poly(methyl methacrylate) nanoparticles by miniemulsion polymerization and in vitro studies.

The aim of this work was the simultaneous encapsulation of magnetic nanoparticles (MNPs) and zinc(II) phthalocyanine (ZnPc) in poly(methyl methacrylate) (PMMA) (MNPsZnPc-PMMA) nanoparticles (NPs) by miniemulsion polymerization and to evaluate the photobiological activity and/or hyperthermia (HPT) against human glioblastoma cells (U87MG). MNPsZnPc-PMMA NPs presented an average diameter of 104 ± 2.5 nm with a polydispersity index (PdI) of 0.14 ± 0.03 and negative surface charge - 47 ± 2.2 mV (pH 7.4 ± 0.1). The encapsulation efficiency (EE%) of ZnPc was 85.7% ± 1.30. The release of ZnPc from PMMA NPs was slow and sustained without the presence of burst effect, indicating a homogeneous distribution of the drug in the polymeric matrix. In the biological assay, MNPsZnPc-PMMA NPs showed considerable cytotoxic effect on U87MG cells only after activation with visible light at 675 nm (photodynamic therapy, PDT) or after application of an alternating magnetic field. The simultaneous encapsulation of MNPs and ZnPc in a drug delivery system with sustained release can be a new alternative for cancer treatment leading to significant tumor regression after minimum doses of heat dissipation and light.

Preclinical pharmacokinetic evaluation of praziquantel loaded in poly (methyl methacrylate) nanoparticle using a HPLC–MS/MS

Praziquantel (PZQ) is the drug recommended by the World Health Organization for treatment of schistosomiasis. However, the treatment of children with PZQ tablets is complicated due to difficulties to adapt the dose and the extremely bitter taste of PZQ. For this reason, poly (methyl methacrylate) nanoparticles loaded with Praziquantel (PZQ-NP) were developed for preparation of a new formulation to be used in the suspension form. For this reason, the main aim of the present study was to evaluate the pharmacokinetic (PK) profile of PZQ-NP, through HPLC-MS/MS assays. Analyses were performed with an Omnisphere C18 column (5.0 μm×4.6 mm×150.0 mm), using a mixture of an aqueous solution containing 0.1 wt% of formic acid and methanol (15:85-v/v) as the mobile phase at a flow rate of 0.800mL/min. Detection was performed with a hybrid linear ion-trap triple quadrupole mass spectrometer with multiple reactions monitoring in positive ion mode via electrospray ionization. The monitored transitions were m/z 313.18>203.10 for PZQ and m/z 285.31>193.00 for the Internal Standard. The method was validated with the quantification limit of 1.00 ng/mL, requiring samples of 25 μL for analyses. Analytic responses were calibrated with known concentration data, leading to correlation coefficients (r) higher than 0.99. Validation performed with rat plasma showed that PZQ was stable for at least 10 months when stored below -70 °C (long-term stability), for at least 17 h when stored at room temperature (RT, 22 °C) (short-term stability), for at least 47 h when stored at room temperature in auto-sampler vials (post-preparative stability) and for at least 8 successive freeze/thaw cycles at -70 °C. For PK assays, Wistar rats, weighing between 200 and 300 g were used. Blood samples were collected from 0 to 24 h after oral administration of single doses of 60 mg/kg of PZQ-NP or raw PZQ (for the control group). PZQ was extracted from plasma by liquid-liquid extraction with terc-butyl methyl ether. The values obtained for maximum concentration (C(max)) and area under curve (AUC) for the PZQ-NP group were about 3 times smaller than the respective values obtained for the control group. However, the time for achieving maximum concentration (T(max)), the elimination constant (Ke) and the half-life time of elimination (T(½β)) were not statistically different. These results suggest that PZQ absorption is probably the rate-limiting step for obtainment of better PK parameters for PZQ-NP. Thus, further studies are needed to understand both the PZQ-NP absorption mechanisms and the drug diffusion process through the polymer matrix in vivo, in order to improve the PZQ-NP release profile.

Study on ethylene polymerization by homogeneous Cp2ZrCl2/methylaluminoxane catalyst system

Abstract Ethylene polymerization was carried out using Cp2ZrCl2 and methylaluminoxane (MAO) as cocatalyst. In this work temperature and [MAO]/[Cp2ZrCl2]([Al]/[Zr]) molar ratio were varied. The highest value of catalyst activity was obtained at 60 °C when [Al]/[Zr] molar ratio =500 was employed. A small increase in catalyst activity was only observed at 60 °C when the [Al]/[Zr] molar ratio was increased to 2000. The produced polyethylenes were characterized by differential scanning calorimetry (DSC) and SEC analysis.

Stability studies of high-stable water-in-oil model emulsions

ABSTRACT Different compositions and emulsification protocols were used to prepare stable water-in-oil (w/o) emulsions. Water, mineral oil, and a mixture of Span 80 and Tween 80 surfactants were combined to form emulsions that can be used as reference for electrolyte-free systems. Here, we have proposed emulsions wherein different properties were evaluated. Electrical conductivity measurements indicated that conductivity increases linearly with increasing surfactant content. The emulsions’ flow curves and viscoelastic behaviors were delineated by rheological measurements. Stability studies by centrifugal testing have shown that smaller the surfactant content, lower the stability, for any used stirring speeds. Furthermore, higher the applied mixing rate to make the emulsion, higher the stability, regardless of the amount of surfactant. Electrical field stability analysis showed, for all systems, that critical electric field (CEF) values were dependent on either surfactant amount and emulsion elastic modulus. GRAPHICAL ABSTRACT