Poly(2-hydroxyethyl methacrylate): A new star polymer

Multiarm star polymers are attractive materials due to their unusual bulk and solution properties. They are considered analogues of dendrimers with a wide range of applications, such as drug delivery, membranes, coatings and lithography.1 The advent of controlled polymerization made possible the existence of this unique class of organic nanoparticles (ONPs).2 Two major synthetic strategies are usually employed in the preparation of star polymers, the core-first and arm-first approaches. The core-first approach involves a controlled living polymerization using a multiarm initiator core while the arm-first methodology is based in the quenching of living polymers with multifunctional coupling agent or bifunctional vinyl compounds. Herein, we present the synthesis and characterization of a new star polymer, the multiarm star poly(2-hydroxyethyl methacrylate). The tetra-armed star polymer was prepared by reversible addition fragmentation chain-transfer (RAFT) polymerization using the core-first approach. The RAFT chain-transfer agent (RAFT CTA) pentaerythritol tetrakis[2-(dodecylthiocarbonothioylthio)-2-methylpropionate] was used as multiarm initiator core were 2-hydroxyethyl methacrylate (HEMA) was polymerized using AIBN as radical initiator. Structural characterization was performed by 1H NMR and FTIR. The new polymer is able to uptake large quantities of organic solvents, forming gels. The rheological behavior of these gels was also investigated.

Fucoidan-based particles for diabetes mellitus treatment

Marine organisms are rich in a variety of materials with potential use in Tissue Engineering and Regenerative Medicine. One important example is fucoidan, a sulfated polysaccharide extracted from the cell wall of brown seaweeds.  Fucoidan is composed by L-fucose, sulfate groups and glucuronic acid. It has important bioactive properties such as anti-oxidative, anticoagulant, anticancer and reducing the blood glucose (1). In this work, the biomedical potential of fucoidan-based materials as drug delivery system was assessed by processing modified fucoidan (MFu) into particles by photocrosslinking using superamphiphobic surfaces and visible light. Fucoidan was modified by methacrylation reaction using different concentrations of methacrylate anhydride, namely 8% v/v (MFu1) and 12% v/v (MFu2). Further, MFu particles with and without insulin (5% w/v) were produced by pipetting a solution of 5% MFu with triethanolamine and eosin-y onto a superamphiphobic surface and then photocrosslinking using visible light (2). The developed particles were characterized to assess their chemistry, morphology, swelling behavior, drug release, insulin content and encapsulation efficiency. Moreover, the viability assays of fibroblast L929 cells in contact with MFu particles showed good adhesion and proliferation up to 14 days. Furthermore, the therapeutic potential of these particles using human beta cells is currently under investigation. Results obtained so far suggest that modified fucoidan particles could be a good candidate for diabetes mellitus therapeutic approaches.  

Analysis of polydicyclopentadiene-metal hybrid adhesive joints for automotive exterior body applications

An exterior body panel solution containing a polydicyclopentadiene skin attached to an interior metallic reinforcement through adhesive bonding is being studied to be applied in the MobiCar bonnet. With this solution is expected to achieve lightness, adequate structural integrity and cost-efficiency. However, there is uncertainty regarding to the bonnet adhesiveness since different metallic materials and adhesive types are being considered for its development. Thus, in this paper, several samples are tested through shear loading with the aim of understanding the loading magnitude expected by using polydicyclopentadiene, steel DC04+ZE and aluminum alloy AW5754-H111 as substrates adhesively bonded by an epoxy or a methacrylate. Methacrylate adhesive have shown greater shear strength in all types of adhesive joints. PDCPD joints presented the highest displacements. Surface degradation was considered adequate over abrading once none strength difference was seen between the different surface treatments. Steel treated by cataphoresis has shown the highest joint interface strength.

Flexible organic–inorganic hybrid layer encapsulation for organic opto-electronic devices

In this work we produce and study the flexible organic–inorganic hybrid moisture barrier layers for the protection of air sensitive organic opto-electronic devices. The inorganic amorphous silicon nitride layer (SiNx:H) and the organic PMMA [poly (methyl methacrylate)] layer are deposited alternatingly by using hot wire chemical vapor deposition (HW-CVD) and spin-coating techniques, respectively. The effect of organic–inorganic hybrid interfaces is analyzed for increasing number of interfaces. We produce highly transparent (∼80% in the visible region) hybrid structures. The morphological properties are analysed providing a good basis for understanding the variation of the water vapor transmission rate (WVTR) values. A minimum WVTR of 4.5 × 10−5g/m2day is reported at the ambient atmospheric conditions for 7 organic/inorganic interfaces. The hybrid barriers show superb mechanical flexibility which confirms their high potential for flexible applications.

Ultrasound enhances lipase-catalyzed synthesis of poly (ethylene glutarate)

The present work explores the best conditions for the enzymatic synthesis of poly (ethylene glutarate) for the first time. The start-up materials are the liquids; diethyl glutarate and ethylene glycol diacetate, without the need of addition of extra solvent. The reactions are catalyzed by lipase B from Candida antarctica immobilized on glycidyl methacrylate-ter-divinylbenzene-ter-ethylene glycol dimethacrylate at 40 °C during 18 h in water bath with mechanical stirring or 1 h in ultrasonic bath followed by 6 h in vacuum in both the cases for evaporation of ethyl acetate. The application of ultrasound significantly intensified the polyesterification reaction with reduction of the processing time from 24 to 7 h. The same degree of polymerization was obtained for the same enzyme loading in less time of reaction when using the ultrasound treatment. The degree of polymerization for long-term polyesterification was improved approximately 8-fold due to the presence of sonication during the reaction. The highest degree of polymerization achieved was 31, with a monomer conversion of 96.77%. The ultrasound treatment demonstrated to be an effective green approach to intensify the polyesterification reaction with enhanced initial kinetics and high degree of polymerization.

Superhydrophobic surfaces as a tool for the fabrication of hierarchical spherical polymeric carriers

Hierarchical polymeric carriers with high encapsulation efficiencies are fabricated via a biocompatible strategy developed using superhydrophobic (SH) surfaces. The carries are obtained by the incorporation of cell/BSA-loaded dextran-methacrylate (DEXT-MA) microparticles into alginate (ALG) macroscopic beads. Engineered devices like these are expected to boost the development of innovative and customizable systems for biomedical and biotechnological purposes.

In-line rheo-optical microstructural characterization of complex polymer systems

Tese de Doutoramento em Ciência e Engenharia de Polímeros e Compósitos.