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

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

Gallium labeled NOTA-based conjugates for peptide receptor-mediated medical imaging

We report a straightforward and efficient synthetic strategy for the synthesis of three model glycine-arginine-glycine-aspartic-glycine (GRGDG) conjugates based on derivatives of NOTA and of their Ga(III) complexes targeted to the integrin αѵβ₃receptor. 71Ga NMR spectroscopy showed that the Ga(III)-labeled conjugates are highly stable in aqueous solution. The 67Ga-labeled conjugates proved to have high kinetic stability and showed a weak but specific binding to the receptors in a U87MG-glioblastoma cell line.Fundação para a Ciência e a Tecnologia (FCT

Revisiting niche fundamentals with Tukey depth

1. The first attempts to describe species ecological niches were simple geometric procedures that depict the niche boundaries directly from environmental data. The convex hull was one of such procedures, popular for its simplicity, clear ecological rational and precise definition of the niche. However, it lacked the ability to differentiate areas of the niche with different probabilities of occurrence according to environmental suitability. 2. We incorporate the Tukey depth, a mathematical tool to measure the centrality of a point within a cloud of points on a multidimensional space, in the convex hull approach to (i) propose a new procedure (CH-Tukey) to estimate species’ environmental suitability, and (ii) estimate niche overlap coherently. In addition to a clear ecological rational and simplicity the CHTukey procedure has a number of attractive features: use of presence-only data; independence from background data; invariance to scale; robustness to outliers; and the decomposition of the niche into a finite number of isosuitability levels, permitting the computation of consistent overlap indices. We illustrate the use of CH-Tukey, using occurrence data of the main Quercus species and subspecies from Western Mediterranean Europe, comparing its outputs with BIOCLIM and MAXENT. 3. Results showed distinct niche geometries among the different approaches. BIOCLIM produced rectilinear niches reflecting the assumption that ecological variables are independent in their action on the species. CHTukey, relaxing this assumption, adjusts niche outer boundary and the inner suitability levels to the known occurrences. MAXENT produced unbounded niche geometries, showing abrupt shifts in the species response to the environmental variables. 4. The niche predictions obtained with geometric approaches, BIOCLIM and CH Tukey, are simpler but better aligned with Hutchinson’s niche concept than those obtained with MAXENT, this latter showing ecologically implausible relationships with the environmental variables. CH-Tukey and the related overlap measures provide an adequate tool to explore niche properties and species-environment relationships

Concordance of three alternative gestational age assessments for pregnant women from four African countries: A secondary analysis of the MIPPAD trial

Background: At times, ultrasound is not readily available in low resource countries in Africa for accurate determination of gestational age, so using alternative methods is pivotal during pregnancy. These assessments are used to aid the risk analysis for an infant and management strategies for premature delivery, if necessary. Currently, date of last menstrual period, fundal height measurements, and the New Ballard Score are commonly used in resource-limited settings. However, concordance of these measures is unknown for sub-Saharan Africa. We obtained data from an open-label randomized controlled trial, to assess the concordance of these alternative assessment methods. The purpose of our study was to determine the agreement between these alternative methods when used in sub-Saharan African populations. Methods: A total of 4,390 pregnant women from Benin, Gabon, Mozambique and Tanzania were included in our analysis. The assessment methods compared were: 1) reported last menstrual period, 2) symphysis-fundal height measurement, and 3) the New Ballard Score. The Bland-Altman method and intraclass correlation coefficient (ICC) were used to test the degree of agreement. Survival range gestational age, used as an inclusion criterion for further analysis, was from 22 to 44 weeks. Findings: Plots showed a lack of agreement between methods and the 95% limits of agreement too wide to be clinically useful. ICC = 0.25 indicated poor agreement. A post-hoc analysis, restricted from 32 to 42 weeks, was done to check for better agreement in this near-term population. The plots and ICC = 0.16 still confirmed poor agreement. Conclusion: The alternative assessments do not result in comparable outcomes and discrepancies are far beyond the clinically acceptable range. Last menstrual period should not be used as the only estimator of gestational age. In the absence of reliable early ultrasound, symphysis-fundal height measurements may be most useful during pregnancy for fetal risk assessment and the New Ballard Score after delivery as a confirmation of these estimations and for further neonatal management. However, promotion of portable ultrasound devices is required for accurate assessment of gestational age in sub-Sahara Africa