Multiresponsive spiropyran-based copolymer: synthesis and characterization

Photochromic copolymers carrying spiropyran side groups have attracted particular attention for potential applications in optical devices, photonic memory and photosensing, as well as, fluorescence imaging.[1] These materials allow overcoming many of the limitations inherent to traditional spiropyran doped polymers, such as, phase separation of the colorant and retardation of the decoloration of the open form.[2] The introduction of light sensitive moieties within responsive polymers has led to the development of sophisticated multiresponsive systems.[3] Block copolymers are important self-assembling systems that can assume a diversity of nanometer-scale morphologies due to the incompatibility and the connectivity constrains between the chemically distinct segments. Therefore, self-assembly of photochromic copolymers in the solid state or in solution allows the development of nanostructured materials. [4] The aim of this research study is the synthesis of a multiresponsive spiropyran-based copolymer, poly(styrene)- co-poly([1´,3´,3´-trimethyl-6-methacryloyloxyspiro(2H-1-benzopyran-2,2´-indoline)]4-vinylbenzoic acid) 2. The functionalized block copolymer poly(styrene)-block-poly(4-vinylbenzoic acid) (PSt-b-P4VBA) 1 synthesized by reversible addition fragmentation chain-transfer (RAFT) polymerization was coupled with 1,3,3-trimethyl-6- hydroxyspiro(2H-1-benzopyran-2,2-indoline). The link between the functionalized block copolymer and spiropyran was successfully obtained by Steglich esterification using DMAP/DCC as catalysts (Scheme 1).n-STeP ProjectNORTE-07-0124-FEDER-000039Programa Operacional Regional do Norte (ON.2)PEst-C/CTM/LA0025/2013 (Strategic Project - LA 25 - 2013-2014

Effect of clay mineral addition on properties of bio-based polymer blends

The effect of clay mineral addition to bio-based blends on morphology and physical properties of thermoplastic starch (TPS) and polypropylene grafted with maleic anhydride (PP-g-MA) was investigated. Blends and nanocomposites containing organoclay, Cloisite 30B, were prepared by melt mixing and characterized by several techniques. X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM, STEM) and dynamic mechanical analysis (DMA) demonstrate a very good dispersion of the clay mineral in the polymer matrix, an increase of polymer compatibility and an improvement of mechanical properties. Biodegradation studies performed in compost revealed that Cloisite 30B addition enhanced the matrix biodegradability. Therefore clay minerals, which can be obtained from natural resources, can be efficiently used to improve the properties of bio-based materials and contribute to sustainability.The authors acknowledge the n-STeP - Nanostructured systems for Tail, with reference NORTE-07-0124-FEDER-000039, supported by the Programa Operacional Regional do Norte (ON.2), PEst-C/CTM/LA0025/2013 (Strategic Project - LA 25 - 2013-2014)

Thermoplastic starch-polypropy/lene reinforced with clay

In this study, bio-based blends of thermoplastic starch (TPS) and polypropylene grafted with maleic anhydride (PP-g-MA) without and with organoclay, Cloisite 30B, were prepared in an internal mixer. A TPS-g-PP copolymer was successfully obtained in melt and its formation was confirmed by SEM. The establishment of this copolymer creates an interpenetrating network leading an intercalated/exfoliated clay nanocomposite. Several analytical, angle X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM, STEM) and dynamic mechanical analysis (DMA) were used to characterize the prepared materials. The nanocomposites mechanical properties were improved, showing an increase of about 11% for the nanocomposite when compared with the neat blend. Biodegradation studies performed in compost revealed good percentage of weight loss for the copolymer with clay addition

Development of silver and clay-starch bio-nanocomposites

Starch, among biopolymers is that had the lowest production cost, wide availability, fully biodegradability and is a renewable agriculture resource. Starch due to its sensitivity to humidity and poor mechanical properties cannot be used in many applications. For that, the dispersion of clays in this material improves their physical and mechanical properties, at very low filler loadings. On the other hand, the incorporation of silver nanoparticles into biocompatible and biodegradable matrices gives antimicrobial properties opening a new field for packaging applications. [...

Sustained gene expression in the retina by improved episomal vectors

Gene and cellular therapies are nowadays part of therapeutic strategies for the treatment of diverse pathologies. The drawbacks associated with gene therapy-low levels of transgene expression, vector loss during mitosis, and gene silencing-need to be addressed. The pEPI-1 and pEPito family of vectors was developed to overcome these limitations. It contains a scaffold/matrix attachment region, which anchors its replication to cell division in eukaryotic cells while in an extrachromosomal state and is less prone to silencing, due to a lower number of CpG motifs. Recent success showed that ocular gene therapy is an important tool for the treatment of several diseases, pending the overcome of the aforementioned limitations. To achieve sustained gene delivery in the retina, we evaluated several vectors based on pEPito and pEPI-1 for their ability to sustain transgene expression in retinal cells. These vectors stably transfected and replicated in retinal pigment epithelial (RPE) cells. Expression levels were promoter dependent with constitutive promoters cytomegalovirus immediate early promoter (CMV) and human CMV enhancer/human elongation factor 1 alpha promoter yielding the highest levels of transgene expression compared with the retina-specific RPE65 promoter. When injected in C57Bl6 mice, transgene expression was sustained for at least 32 days. Furthermore, the retina-specific RPE65 promoter showed higher efficiency in vivo compared to in vitro. In this study, we demonstrate that by combining tissue-specific promoters with a mitotic stable system, less susceptible to epigenetic silencing such as pEPito-based plasmids, we can achieve prolonged gene expression and a sustained therapeutic effect.Fundacao para a Ciencia e Tecnologia, Portugal [PEst/OE/EQB-LA 0023/2013, SFRH/BD/76873/2011, SFRH/BD/70318/2010, PTDC/SAU/BEB/098475/2008]; European Union [PIRG-GA-2009-249314

Entrapment of CdTe quantum dots in polymeric micelles

Semiconductor quantum dots (QDs) have attracted increasing interest to their unique sizedependent optical and electronic properties. Some of the most promising applications are imaging and biological sensing, acting as fluorescent probes.[1] However, for these purposes QDs need to be attached to other species. Thus, amphiphilic polymers, displaying both hydrophobic and hydrophilic regions, are interesting systems to encapsulate QDs.[2] The entrapment of hydrophobic QDs into surfactant micelles results in the formation of fluorescent nanoparticles composed by a QD core and a surfactant shell. This results in improved QDs dispersion in biological environments, lowering their toxicity. The present work investigates the entrapment of CdTe QDs in micelles formed by poly(acrylic acid) macroRAFT (PAA), a new water soluble amphiphilic polymer. The results obtained indicate that the PAA/QDs ration plays an important role not only in the dispersion of the nanoparticles in aqueous systems but also in the optical properties of the QDs

Polymeric micellar drug carriers with fluorescent properties

Self-assembling polymeric surfactants, based on amphiphilic block copolymers into nanosized aggregates in aqueous solution, are of great interest in the biomedical fields as one class of promising carrier systems, for drug delivery, gene therapy and diagnostic biosensors.[1] The incorporation of fluorescent probes into polymeric micelles has been fulfilled either by physically encapsulation or chemically attachment of fluorophores. [2] These micelle-based fluorescent probes not only facilitate better dispersion of fluorophores in biological environments, but also reduce their cytotoxicity by avoiding direct contact with normal cells or tissues. In this work we present new water soluble amphiphilic polymers, poly(acrylic acid) macroRAFT (PAA) 1 and poly(acrylic acid)-block-poly(9-vinylanthracene) (PAA-b-P9VA) 2, for the production of the mixed fluorescent micelles. Fluorescence assays were performed to monitoring the effect of their ratio on the formation of mixed micelles and to determine 1’s critical micelle concentration (cmc). The cmc was also evaluated by surface tension measurements

Cellulose acetate/carbon nanotube composites by melt mixing

Cellulose acetate (CA) is produced from a natural polymer and presents excellent properties, finding applications in a variety of areas. Unlike cellulose, CA is melt processable and may be molded into parts and formed into fibers or films. In this context, the production of conductive CA composites that may be processable and integrated into parts to provide specific functionalities is an area of increasing interest. The present work aims to prepare electrically conductive composites based on CA and carbon nanotubes (CNTs) by melt mixing. The nanocomposites were produced with pure and pyrrolidine-functionalized nanotubes, using a batch mixer and a twin-screw extruder. The morphology of carbon nanotube dispersion, the rheological behavior and the electrical conductivity of the final composites were evaluated. Rheological percolation was achieved for the composites with 0.5 wt% of CNT—both pure and functionalized—produced by extrusion; while electrical percolation was observed only for the composites with pure CNT.The authors acknowledge the Portuguese Foundation of Science and Technology (SFRH/BD/81711/2011 and PEst-C/CTM/LA0025/2011) and n-SteP – Nanostructured Systems for Tailored Properties, with reference NORTE-07-0124-FEDER-000039, supported by the Programa Operacional Regional do Norte (ON.2).info:eu-repo/semantics/publishedVersio

The influence of melt mixing on the stability of cellulose acetate and its carbon nanotube composites

Cellulose derivatives, such as cellulose acetate (CA), are commonly used due to their ease of processing. These polymers present interesting mechanical properties and biodegradability, but low thermal stability under melt processing conditions. Composites of carbon nanotubes (CNTs) and cellulose derivatives are expected to present enhanced properties, depending on the effect of nanotubes on polymer structure and thermal properties. This work aims to investigate the influence of melt mixing on the stability of CA and its CNT composites. Composites with 0 wt%, 0.1 wt% and 0.5 wt% CNTs, as received and functionalized with pyrrolidine groups, were prepared using a batch mixer and an extruder. Chain scission of CA occurred during processing, but the effect was considerably reduced in the presence of CNTs. The incorporation of small amounts of CNTs (with or without functionalization) decreased polymer degradation by thermomechanical effects induced during polymer processing.The authors acknowledge the Portuguese Foundation for Science and Technology (SFRH/ BD/81711/2011) and n-STeP – Nanostructured systems for Tailored Properties, with reference NORTE-07-0124- FEDER-000039, supported by the Programa Operacional Regional do Norte (ON.2).info:eu-repo/semantics/publishedVersio