An interesting ligand for the preparation of luminescent plastics : the picrate ion

Electrolytes formed with poly(oxyethylene), POE, and europium picrate [Eu(pic)2(OH2)6]pic.6H2O (where pic denotes the picrate anion) or simply Eu(pic)3xH2O, have been represented by POEnEu(pic)3xH2O (where n represents the molar ratio of (OCH2CH2) units per Eu3+ ion). Materials with n ranging from 133 to 11 have been examined. A tentative attribution of the absorption bands of the mid-infrared spectra is presented. The spectral changes detected in the mid-infrared region and the modifications in the XRD patterns at increasing salt content show that PEOnEu(pic)3xH2O exerts an effective plasticizing role which leads to the complete supression of crystallinity at n = 11. The emission spectra of the complexes and their signature in the vC-O spectral region provide conclusive evidence that the Eu3+ ions are coordinated to the oxygen atoms of the polyether chains over the whole range of compositions studied. The photoluminescence spectra of the PEOnEu(pic)3xH2O electrolytes indicate that the Eu3+/ether oxygen complexation occurs with concomittant partial substitution of the water molecules from the cation coordination shell. The luminescence data obtainedFundação para a Ciência e a Tecnologia (FCT

Dye-sensitized solar cells: A safe bet for the future.

This review describes the main features of dye-sensitized solar cells (DSCs) and highlights recent breakthroughs in this promising thin-film photovoltaic (PV) technology. After a brief presentation of the commercially available technologies, the general operation principles and the most relevant characteristics of DSCs are summarized. Recent major advances in high efficiency sensitizers, nanostructured semiconductors and robust electrolytes offer an opportunity for DSCs integration into the marketplace. With attractive features, like low-cost potential, simple processing, wide range of applicability - from low-power electronics to semi-transparent windowpanes for electricity generation - and good performance under typical operating conditions, these cells are one step from large-scale commercialization. We describe major strategies that are under way to make DSCs a key technology in the future PV paradigm

Matrix Assisted Formation of Ferrihydrite Nanoparticles in a Siloxane/Poly(Oxyethylene) Nanohybrid

Matrix-assisted formation of ferrihydrite, an iron oxide hydroxide analogue of the protein ferritin-core, in a sol-gel derived organic-inorganic hybrid is reported. The hybrid network (named di-ureasil) is composed of poly(oxyethylene) chains of different average polymer molecular weights grafted to siloxane domains by means of urea cross-linkages and accommodates ferrihydrite nanoparticles. Magnetic measurements, Fourier transform infrared and nuclear magnetic resonance spectroscopy reveal that the controlled modification of the polymer molecular weight allows the fine-tuning of the ability of the hybrid matrix to assist and promote iron coordination at the organic-inorganic interface and subsequent nucleation and growth of the ferrihydrite nanoparticles whose core size (2-4 nm) is tuned by the amount of iron incorporated. The polymer chain length, its arrangement and crystallinity, are key factors on the anchoring and formation of the ferrihydrite particles.Comment: 7 pages, 6 figures. To be published in J. Mater. Che

Data cloning estimation for asymmetric stochastic volatility models

The paper proposes the use of data cloning (DC) to the estimation of general asymmetric stochastic volatility (ASV) models with flexible distributions for the standardized returns. These models are able to capture the asymmetric volatility, the leptokurtosis and the skewness of the distribution of returns. Data cloning is a general technique to compute maximum likelihood estimators, along with their asymptotic variances, by means of a Markov chain Monte Carlo (MCMC) methodology. The main aim of this paper is to illustrate how easily general ASV models can be estimated and consequently studied via data cloning. Changes of specifications, priors and sampling error distributions are done with minor modifications of the code. Using an intensive simulation study, the finite sample properties of the estimators of the parameters are evaluated and compared to those of a benchmark estimator that is also user-friendly.The results show that the proposed estimator is computationally efficient and robust, and can be an effective alternative to the exiting estimation methods applied to ASV models. Finally, we use data cloning to estimate the parameters of general ASV models and forecast the one-step-ahead volatility of S&P 500 and FTSE-100 daily returns

Preparation of well-dispersed chitosan/alginate hollow multilayered microcapsules for enhanced cellular internalization

Hollow multilayered capsules have shown massive potential for being used in the biomedical and biotechnology fields, in applications such as cellular internalization, intracellular trafficking, drug delivery, or tissue engineering. In particular, hollow microcapsules, developed by resorting to porous calcium carbonate sacrificial templates, natural-origin building blocks and the prominent Layer-by-Layer (LbL) technology, have attracted increasing attention owing to their key features. However, these microcapsules revealed a great tendency to aggregate, which represents a major hurdle when aiming for cellular internalization and intracellular therapeutics delivery. Herein, we report the preparation of well-dispersed polysaccharide-based hollow multilayered microcapsules by combining the LbL technique with an optimized purification process. Cationic chitosan (CHT) and anionic alginate (ALG) were chosen as the marine origin polysaccharides due to their biocompatibility and structural similarity to the extracellular matrices of living tissues. Moreover, the inexpensive and highly versatile LbL technology was used to fabricate core-shell microparticles and hollow multilayered microcapsules, with precise control over their composition and physicochemical properties, by repeating the alternate deposition of both materials. The microcapsules' synthesis procedure was optimized to extensively reduce their natural aggregation tendency, as shown by the morphological analysis monitored by advanced microscopy techniques. The well-dispersed microcapsules showed an enhanced uptake by fibroblasts, opening new perspectives for cellular internalization.publishe

Chitosan membranes containing micro or nano-size bioactive glass particles : evolution of biomineralization followed by in-situ dynamic mechanical analysis

A newfamilyofbiodegradablepolymer/bioactiveglass(BG)compositematerialshas emergedbasedontheavailabilityofnano-sizedbioactiveparticles.Suchnovelbiocompo- sites canhaveenhancedperformance,intermsofmechanicalpropertiesandbioactivity, and theycanbedesignedtobeusedinboneregenerationapproaches. In thiswork,membranesofchitosan(CTS)andchitosanwithbioactiveglass(BG)both micron andnanosizedparticles(CTS/mBG,CTS/nBG,respectively)werepreparedby solvent casting.Microstructuralandmechanicalpropertieswereevaluatedinorderto compare theeffectsoftheincorporationofmicro(mBG) andnano(nBG)particlesinthe chitosan matrix. In vitro bioactivity testswereperformedtocharacterizetheapatitelayer that isformedonthesurfaceofthematerialafterbeingimmersedinsimulatedbodyfluid (SBF). Thebiomineralizationprocessonthebiomaterialswasalsofollowedusingnon- conventionaldynamicmechanicalanalysis(DMA),bothonlineandoffline.InsuchDMA experiments,thechangeinthestoragemodulus, E0, andthelossfactor,tan d, were measured asafunctionoftheimmersiontimeinSBF.TheresultsdemonstratedthatCTS/ nBG membranespossessenhancedmechanicalpropertiesandhigherbioactivityin comparisonwiththeCTS/mBG membranes.SuchresultssuggestthepotentialofnBGfor the developmentofbioactivecompositesforboneregenerationapplications.This work was financially supported by Foundation for Science and Technology (FCT) by the projects PTDC/QUI/69263/2006, PTDC/CTM-BPC/112774/2009 and, through the scholarship SFRH/BD/64601/2009 granted to Sofia G. Caridade. The authors acknowledge Dr D. Mohn and Prof. W. Stark (Em Zurich) for providing the nBG particles used

Erratum: Development of Poly(l-Lactic Acid)-Based Bending Actuators. Polymers 2020, 12, 1187

The authors wish to make a change to their published paper [1]. In the original manuscript, there is a mistake in a sentence in Section 3.5, on page 10. Two words “anions and cations” were reverted by mistake. The corrected sentence is shown below: The strain developed as a response to the applied electrical field results from the diffusion of the ions and migration to the positive (anions) and negative (cations) electrode layers, and subsequent accumulation close to the electrodes. The authors apologize for any inconvenience caused, and the change does not affect the scientific results. The manuscript will be updated, and the original will remain online on the article webpage at https://www.mdpi.com/2073-4360/12/5/1187.(undefined

Development of poly(l-Lactic Acid)-based bending actuators

This work reports on the development of bending actuators based on poly(l-lactic acid) (PLLA)/ionic liquid (IL) blends, through the incorporation of 40% wt. of the 1-ethyl-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][TFSI]) IL. The films, obtained by solvent casting at room temperature and 50 °C, were subjected to several post-thermal treatments at 70, 90, 120 and 140 °C, in order to modify the crystallinity of the films. The influence of the drying temperature and of [Emim][TFSI] blending on the morphological, structural, mechanical and electrical properties of the composite materials were studied. The IL induced the formation of a porous surface independently of the processing conditions. Moreover, the [Emim][TFSI] dopant and the post-thermal treatments at 70 °C promoted an increase of the degree of crystallinity of the samples. No significant changes were observed in the degree of crystallinity and Young Modulus for samples with thermal treatment between 70 and 140 °C. The viability of the developed high ionic conductive blends for applications as soft actuators was evaluated. A maximum displacement of 1.7 mm was achieved with the PLLA/[Emim][TFSI] composite prepared at 50 °C and thermally treated at 140 °C, for an applied voltage of 10 Vpp, at a frequency of 100 mHz. This work highlights interesting avenues for the use of PLLA in the field of actuators.The authors thank the FCT—Fundação para a Ciência e Tecnologia—for financial support under the Strategic Funding UID/FIS/04650/2020, and PEST-C/QUI/UIO686/2019, the Associated Laboratory Research Unit for Green Chemistry, Technologies and Clean Processes, LAQV (financed by national funds from FCT/MEC, UID/QUI/50006/2020 and ERDF under the PT2020, POCI-01-0145-FEDER-007265) and projects PTDC/BTM-MAT/28237/2017 and PTDC/EMD-EMD/28159/2017. DMC and LCF also thank the grants SFRH/BPD/121526/2016 and SFRH/BD/145345/2019, respectively