Carla Vilela

The quest for sustainable polyesters – insights into the future

Polyesters from renewable resources are an expanding area with a burgeoning scientific activity, nevertheless little has been reviewed about this particular class of polymers. The present appraisal intends to contribute to fill this literature gap by reviewing recent aspects related to the most promising renewable-based polyesters. Emphasis will be placed on bio-based polyesters that, given their comparable properties, may replace polymers derived from fossil fuel feedstock, and on bio-based polyesters with completely innovative properties for novel applications. Furthermore, the sources of renewable monomers will also be reviewed, together with the most relevant eco-friendly synthetic approaches used in polycondensation reactions leading to polyesters.

Biobased polyesters and other polymers from 2,5-furandicarboxylic acid: a tribute to furan excellency

Motivated by the general concern about sustainability and environmental issues, an intense search for renewable-based polymers has grown exponentially in recent years. This search definitely spotlighted polyesters derived from 2,5-furandicarboxylic acid, among other polymers, as some of the most promising, especially due to the resemblance of this renewable monomer to the well-known petroleum-based terephthalic acid, as well as owing to the possibility of preparing innovative materials. The huge number of recent papers and patents about this family of polymers explore aspects as diverse as synthesis with other renewable-based monomers, leading to the preparation of materials with enhanced thermo-mechanical, biodegradability and liquid crystalline properties, among other features. Additional aspects pursued in such studies are innovation in the synthetic approaches or their optimisation, as well as the development of applications for everyday-life objects for example packaging materials, especially bottles, textiles, coating, and toners, among many other uses. Despite this intense activity, little has been reviewed recently about this unique family of polyesters or derived polymers, as the only reviews on the subject date back to the last century. In this perspective, the present review aims at contributing to filling this literature gap, covering recent aspects related with challenges in developing polyesters, polyamides, or other polymers from 2,5-furandicarboxylic acid and their precursors. Emphasis is placed on monomer synthesis, polymerisation reactions, catalysts and applications.

Ultra-high performance liquid chromatography coupled to mass spectrometry applied to the identification of valuable phenolic compounds from Eucalyptus wood

Ultra-high performance liquid chromatography (UHPLC) was applied for the first time in the analysis of wood extracts. The potential of this technique coupled to ion trap mass spectrometry in the rapid and effective detection and identification of bioactive components in complex vegetal samples was demonstrated. Several dozens of compounds were detected in less than 30min of analysis time, corresponding to more than 3-fold reduction in time, when compared to conventional HPLC analysis of similar extracts. The phenolic chemical composition of Eucalyptus grandis, Eucalyptus urograndis (E. grandis×E. urophylla) and Eucalyptus maidenii wood extracts was assessed for the first time, with the identification of 51 phenolic compounds in the three wood extracts. Twenty of these compounds are reported for the first time as Eucalyptus genus components. Ellagic acid and ellagic acid-pentoside are the major components in all extracts, followed by gallic and quinic acids in E. grandis and E. urograndis and ellagic acid-pentoside isomer, isorhamnetin-hexoside and gallic acid in E. maidenii. The antioxidant scavenging activity of the extracts was evaluated, with E. grandis wood extract showing the lowest IC50 value. Moreover, the antioxidant activity of these extracts was higher than that of the commercial antioxidant BHT and of those of the corresponding bark extracts. These results, together with the phenolic content values, open good perspectives for the exploitation of these renewable resources as a source of valuable phenolic compounds.

Protein-based materials: from sources to innovative sustainable materials for biomedical applications

Proteins display an essential role in numerous natural systems due to their structural and biological properties. Given their unique properties, proteins have been thoroughly investigated in the last few decades, offering a myriad of solutions for the development of innovative biomaterials, including films, foams, composites and gels, in particular for biomedical applications such as drug delivery systems, biosensors and scaffolds for tissue regeneration. In this context, this review intends to give a general overview of the potential of protein based materials within the sustainable polymers context, covering aspects ranging from protein types, selection/isolation to properties of protein based (nano)materials and biomedical applications, passing through preparation methodologies of materials.

Reversible polymerization of novel monomers bearing furan and plant oil moieties: a double click exploitation of renewable resources

Monomers based on plant oil derivatives bearing furan heterocycles appended through thiol-ene click chemistry were prepared and, subsequently, polymerized via a second type of click reaction, i.e. the Diels–Alder (DA) polycondensation between furan and maleimide complementary moieties. Two basic approaches were considered for these DA polymerizations, namely (i) the use of monomers with two terminal furan rings in conjunction with bismaleimides (AA + BB systems) and (ii) the use of a protected AB monomer incorporating both furan and maleimide end groups. This study clearly showed that both strategies were successful, albeit with different outcomes, in terms of the nature of the ensuing products. The application of the retro-DA reaction to these polymers confirmed their thermoreversible character, i.e. the clean-cut return to their respective starting monomers, opening the way to original macromolecular materials with interesting applications, like mendability and recyclability.

Nanostructured bacterial cellulose-poly(4-styrene sulfonic acid) composite membranes with high storage modulus and protonic conductivity.

The present study reports the development of a new generation of bio-based nanocomposite proton exchange membranes based on bacterial cellulose (BC) and poly(4-styrene sulfonic acid) (PSSA), produced by in situ free radical polymerization of sodium 4-styrenesulfonate using poly(ethylene glycol) diacrylate (PEGDA) as cross-linker, followed by conversion of the ensuing polymer into the acidic form. The BC nanofibrilar network endows the composite membranes with excellent mechanical properties at least up to 140 °C, a temperature where either pure PSSA or Nafion are soft, as shown by dynamic mechanical analysis. The large concentration of sulfonic acid groups in PSSA is responsible for the high ionic exchange capacity of the composite membranes, reaching 2.25 mmol g(-1) for a composite with 83 wt % PSSA/PEGDA. The through-plane protonic conductivity of the best membrane is in excess of 0.1 S cm(-1) at 94 °C and 98% relative humidity (RH), decreasing to 0.042 S cm(-1) at 60% RH. These values are comparable or even higher than those of ionomers such as Nafion or polyelectrolytes such as PSSA. This combination of electric and viscoelastic properties with low cost underlines the potential of these nanocomposites as a bio-based alternative to other polymer membranes for application in fuel cells, redox flow batteries, or other devices requiring functional proton conducting elements, such as sensors and actuators.

A Double Click Strategy Applied to the Reversible Polymerization of Furan/Vegetable Oil Monomers

This investigation describes preliminary results related to the preparation of monomers based on vegetable oil derivatives bearing furan heterocycles appended through thiol-ene click chemistry, and their subsequent polymerization via the Diels-Alder (DA) polycondensation between furan and maleimide complementary moieties, i.e. a second type of click chemistry. Following the optimization of these interactions with model compounds, two basic approaches were considered for these DA polymerizations, namely (i) the use of monomers with two terminal furan rings in conjunction with bismaleimides (AA + BB systems) and (ii) the use of AB monomers incorporating both furan and maleimide end-groups. This ongoing study clearly showed that both approaches were successful, albeit with different outcomes, in terms of the nature of the products. The application of the retro-DA reaction confirmed their thermoreversible character, i.e. the clean-cut return to their respective starting monomers.

Chlorophyta and Rhodophyta macroalgae: A source of health promoting phytochemicals

A detailed study of the lipophilic composition of Codium tomentosum, Ulva lactuca, Gracilaria vermiculophylla and Chondrus crispus macroalgae cultivated in the Portuguese coast was carried out by gas chromatography-mass spectrometry before and after alkaline hydrolysis. Their long-chain aliphatic alcohols and monoglycerides compositions are reported for the first time. Additionally, other new compounds were also identified: phytol and neophytadiene in C. tomentosum, U. lactuca and G. vermiculophylla and stigmasterol, α-tocopherol and 24-methylenecholesterol in C. tomentosum. The lipophilic fraction of the studied macroalgae are mainly constituted by fatty acids (110.1-1030.5mgkg(-1) of dry material) and sterols (14.8-1309.1mgkg(-1) of dry material). C. tomentosum showed to be a valuable source of stigmasterol (1229.0mgkg(-1) of dry material) and α-tocopherol (21.8mgkg(-1) of dry material). These results are a relevant contribution for the valorisation of these macroalgae species as sources of valuable phytochemicals.

Multilayered materials based on biopolymers as drug delivery systems.

ABSTRACT Introduction: The design of efficient therapeutic delivery devices has become a tremendously active area of research with a strong contribution from the layer-by-layer (LbL) technology. The application of this simple yet firmly established technique for the design of drug reservoirs originates a multitude of multilayered systems of tailored architecture and with a high level of control of drug administration. Areas covered: This review will focus on the most recent and original research on LbL assemblies based on biopolymers including polysaccharides, polypeptides and proteins, with potential use in drug delivery. Herein, drug reservoirs consisting of multilayered planar films and capsules will be examined with emphasis on the ones benefiting from the non-cytotoxic and biocompatible nature of biopolymers, which are suitable to load, protect and release a high payload of toxic and fragile drugs. Expert opinion: The combination of biopolymers with LbL technology has undergone extensive research, still, there is a multitude of R&D opportunities for the design of smart drug delivery systems with distinct multilayered morphologies, low immunological response, non-invasive drug release devices, as well as the design of theranostic systems combining diagnostics and therapeutic features. Further developments in terms of scaling towards mass production in the pharmaceutical industry are expected in the long-term.

Poly(N-methacryloyl glycine)/nanocellulose composites as pH-sensitive systems for controlled release of diclofenac

The present study reports the development of non-cytotoxic and pH-sensitive nanostructured membranes consisting of a polymer with amino acid pending moieties and bacterial nanocellulose (BC). The nanocomposites were prepared through a simple methodology under green reaction conditions. The obtained materials display good thermal stability (up to 200°C), viscoelastic (storage modulus>700MPa) and mechanical (Youngs modulus=3.5-4.9GPa) properties, together with high water uptake capacity. The results of the in vitro MTT assay showed that the nanocomposites are non-cytotoxic to HaCaT cells for 72h. The in vitro release profile of diclofenac sodium salt (DCF) from the nanocomposites into simulated body fluids at different pH values demonstrates the pH-responsive behaviour of these materials. Besides, DCF is mainly retained in the nanocomposites at pH 2.1 and released at pH 7.4, revealing their potential for the controlled release of DCF in dermal as well as in oral drug delivery applications.