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

Development of iridium porphyrin arrays by axial coordination trough N-bidentate ligand: Synthesis and evaluation of the optical, electrochemical and thermal properties

Several organic compounds have been used in optoelectronics devices; porphyrins, due to their interesting optical and electronic properties, have shown an attractive potential to be used on molecular electronics. Among other advantages, porphyrins easily coordinate with several metal ions, which allows the assembly with peripheral or axial ligands introducing new properties to the supramolecular porphyrin. In this work, a new metalloporphyrin system with 5,10,15,20-(tetra-p-tolyl)porphyrin (ttp) and iridium(III) where 4,4’-bipyridine (bpy) coordinate in the axial positions was successfully synthetized, through the formation of “shish kebab” structures. This new compound was characterized through ultraviolet-visible, proton nuclear magnetic resonance, Fourier-transform infrared and Raman spectroscopies, thermogravimetry, differential scanning calorimeter and cyclic voltammetry. The introduction of the bpy on the metalloporphyrin moiety exhibited important influence on the optical, thermal and electrochemical properties.The authors acknowledge the Portuguese Foundation of Science and Technology (TSSiPRO – TECHNOLOGIES FOR SUSTAINABLE AND SMART INNOVATIVE PRODUCTS – NORTE-01-0145-FEDER-000015) and UID/CTM/50025/2013 for the financial support.info:eu-repo/semantics/publishedVersio

Design of assemblies based on polymer-coated quantum dots and organic dye

During last years, photophysical properties of complexes of semiconductor quantum dots (QDs) with organic dyes have attracted increasing interest. The development of different assemblies based on QDs and organic dyes allows to increase the range of QDs applications, which include imaging, biological sensing and electronic devices.1 Some studies demonstrate energy transfer between QDs and organic dye in assemblies.2 However, for electronic devices purposes, a polymeric matrix is required to enhance QDs photostability. Thus, in order to attach the QDs to the polymer surface it is necessary to chemically modify the polymer to induce electronic charges and stabilize the QDs in the polymer. The present work aims to investigate the design of assemblies based on polymer-coated QDs and an integrated acceptor organic dye. Polymethylmethacrylate (PMMA) and polycarbonate (PC) were used as polymeric matrices, and nile red as acceptor. Additionally, a PMMA matrix modified with 2-mercaptoethylamine is used to improve the attachment between both the donor (QDs) and the acceptor (nile red), as well as to induce a covalent bond between the modified PMMA and the QDs. An enhancement of the energy transfer efficiency by using the modified PMMA is expected and the resulting assembly can be applied for energy harvesting

Sustainable materials based on cellulose from food sector agro-wastes

Biopolymers exhibit unique properties and can be produced from plants' and crops' wastes. Cellulose has been used for the production of sustainable materials, nevertheless due to the difficulty inherent to its extraction, several methods have been studied in order to optimize the process. Therefore, this paper reports the extraction of natural polymers from food sector agro-food wastes, including cellulose, following a green chemistry aproach. The cellulose extracted from pumpkin peel was acetylated and dispersed in a polylactic acid (PLA) matrix. The developed materials were characterized in terms of their structure, morphology and thermal stability. The results demonstrated the efficient chemical modification of cellulose and confirmed its good dispersion within the PLA matrix.This work is funded by FEDER funds through the COMPETE 2020 Programme and National Funds through FCT-Portuguese Foundation for Science and Technology under the project UID/CTM/50025/2013

Effect of polymeric matrix on morphology and photoelectric properties of polymer-quantum dots nanocomposites

Recently, CdTe semiconductor quantum dots (QDs) have attracted great interest due to their unique properties [1]. Their dispersion into polymeric matrices would be very for several optoelectronics applications. Despite its importance, there has been relatively little work done on charge transport in the QD polymeric films [2], which is mainly affected by their structural and morphological properties. In the present work, polymer-quantum dot nanocomposites films based on optically transparent polymers in the visible spectral range and CdTe QDs with controlled particle size and emission wavelength, were prepared via solvent casting. Photoluminescent (PL) measurements indicate different emission intensity of the nanocomposites. A blue shift of the emission peak compared to that of QDs in solution occurred, which is attributed to the QDs environment changes. The morphological and structural properties of the CdTe nanocomposites were evaluated. Since better QDs dispersion was achieved, PMMA seemed to be the most promising matrix. Electrical properties measurements indicate an ohmic behavior

High fluorescent water soluble CdTe quantum dots—a promising system for light harvesting applications

The entrapment of quantum dots (QDs) in the inner part of micelles formed by surfactant polymers is a powerful methodology to prepare stable and photoluminescent core nanoparticles with enhanced optical properties. These features are crucial for the application of QDs in the design of hybrid assemblies for light harvesting applications, where energy transfer processes are required. The present work was focused on the synthesis of a surfactant homopolymer, poly (acrylic acid) (PAA) macroRAFT, to be used as a stabilizer of hydrophobic cadmium telluride (CdTe) QDs in aqueous solution. PAA macroRAFT was synthesized by reversible addition-fragmentation chain-transfer (RAFT) polymerization in a single chemical reaction. Its micelles were used to entangle and entrap hydrophobic CdTe QDs, with different molar ratio of polymer and QDs. The morphology and optical properties of the entrapped QDs were determined. The results showed that PAA macroRAFT is able to form micelles with a critical micelle concentration of 2.08 mg/mL. It was also noticed that the molar ratio of polymer and QDs have high influence on the QDs' morphology and their optical properties. The QDs' photoluminescence quantum yield was enhanced approximately 23% upon their entrapment in PAA macroRAFT micelles, using 60 equivalents of polymer. Moreover, while in solution, QDs are well-dispersed, having a 3.5 nm diameter, upon being entrapped in the micelles, tend to form clusters with a size around 100 nm.The authors acknowledge n-STeP-Nanostructured systems for Tailored Performance, 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).info:eu-repo/semantics/publishedVersio

Characterisation of microbial attack on archaeological bone

As part of an EU funded project to investigate the factors influencing bone preservation in the archaeological record, more than 250 bones from 41 archaeological sites in five countries spanning four climatic regions were studied for diagenetic alteration. Sites were selected to cover a range of environmental conditions and archaeological contexts. Microscopic and physical (mercury intrusion porosimetry) analyses of these bones revealed that the majority (68%) had suffered microbial attack. Furthermore, significant differences were found between animal and human bone in both the state of preservation and the type of microbial attack present. These differences in preservation might result from differences in early taphonomy of the bones. © 2003 Elsevier Science Ltd. All rights reserved