Controlled drug release from hydrogels for contact lenses: drug partitioning and diffusion

Optimization of drug delivery from drug loaded contact lenses assumes understanding the drug transport mechanisms through hydrogels which relies on the knowledge of drug partition and diffusion coefficients. We chose, as model systems, two materials used in contact lens, a poly-hydroxyethylmethacrylate (pHEMA) based hydrogel and a silicone based hydrogel, and three drugs with different sizes and charges: chlorhexidine, levofloxacin and diclofenac. Equilibrium partition coefficients were determined at different ionic strength and pH, using water (pH 5.6) and PBS (pH 7.4). The measured partition coefficients were related with the polymer volume fraction in the hydrogel, through the introduction of an enhancement factor following the approach developed by the group of C. J. Radke (Kotsmar et al., 2012; Liu et al., 2013). This factor may be decomposed in the product of three other factors EHS, Eel and Ead which account for, respectively, hard-sphere size exclusion, electrostatic interactions, and specific solute adsorption. While EHS and Eel are close to 1, Ead > > 1 in all cases suggesting strong specific interactions between the drugs and the hydrogels. Adsorption was maximal for chlorhexidine on the silicone based hydrogel, in water, due to strong hydrogen bonding. The effective diffusion coefficients, De, were determined from the drug release profiles. Estimations of diffusion coefficients of the non-adsorbed solutes D = De × Ead allowed comparison with theories for solute diffusion in the absence of specific interaction with the polymeric membrane.info:eu-repo/semantics/publishedVersio

Produção Sustentável em Ambiente Protegido de Flores para Uso Humano

As crescentes preocupações ambientais e as novas tendências pelo consumo nutricional orgânico (mais saudável e livre de produtos químicos) estão a influenciar os consumidores nas escolhas que fazem, ao nível dos seus hábitos e na atitude em relação ao meio ambiente. Este paradigma tem induzido os agricultores com produções em ambientes protegidos, a um interesse renovado na geração de flores comestíveis, para uso cosmético e medicinal, como forma de procurar alternativas aos cultivares tradicionais de procura sazonal, por um mix de produtos de consumo regular e que, simultaneamente, proporcionem boa rentabilidade. O recurso a ambientes protegidos, procura ir de encontro às expectativas dos consumidores sensibilizados que estão, para uma agricultura sustentável, quer ao nível da segurança dos produtos, quer ao nível do impacto ambiental resultante da atividade gerada. Embora os requisitos culturais para a produção de flores para uso humano sejam semelhantes aos das flores ornamentais, exige-se para estas, uma produção especializada, uma vez que são cultivadas sem qualquer tipo de agrotóxico ou produto químico. Sendo o recurso a agroquímicos nulo, importa investir em tecnologias relacionadas com a produção em ambiente protegido, nomeadamente no que se refere à temperatura, humidade, irrigação e radiação solar. Os principais custos associados a culturas produzidas em estufas estão relacionados com a energia e o ambiente. Ressalta assim, a preocupação crescente atribuída a estas duas componentes, pelo impacto que representam na imagem e na competitividade das empresas produtoras. Esta condição é ainda mais relevante, quando falamos de floricultura para uso humano, cuja produção se rege por superiores exigências em climatização com temperaturas médias de 11°C no inverno e de 26°C no verão, o que eleva os consumos energéticos e por conseguinte, com substancial impacto ambiental. Estes pressupostos induzem os empresários do setor, a realizar os seus investimentos, em zonas com climas mais moderados, cientes de que, esta circunstância deprecia os encargos associados à produção e sustentabilidade. As estufas selecionadas para a realização desta investigação localizam-se no Ribatejo/Portugal e protegem uma área de 24.000m². O sistema de aquecimento é composto por uma caldeira com uma potência nominal de 2.000kW, cuja energia primária é a biomassa sólida. A gestão dos vários parâmetros, relativos ao ambiente interno é assegurada, por sensores instalados nas estufas e em boa parte pela ventilação natural. Avaliaram-se os padrões construtivos, assim como, consumos de energia elétrica, poder calorifico do combustível, combustão da caldeira, emissões gasosas e ambiente no interior da infraestrutura. Após avaliação das condições de funcionamento propôs-se um conjunto de medidas de melhoria, nomeadamente, combustível a utilizar na caldeira, armazenagem da biomassa, isolamento térmico de tubagens, elementos construtivos e equipamentos de inércia térmica, que no seu conjunto constituem, um superior desempenho energético e ambiental desta estrutura. Também se propôs a instalação de um sistema fotovoltaico em regime de autoconsumo, com o objetivo de contribuir para a eficiência energética e ambiental, neste tipo de produções agrícolas. Complementarmente a estas ações realizou-se um estudo económico da viabilidade dos investimentos.info:eu-repo/semantics/publishedVersio

Diffusion coefficients of perfluorinated n-alcohols in water and heavy water: experiment and computer simulation

Fluorinated surfactants find nowadays many industrial applications due to their enhanced ability to lower surface tension in aqueous solutions [1]. As a result of their extensive use, emissions of fluorinated surfactants became frequent and, because of their persistent character, have been increasingly found in the environment [2]. Both the development of theoretical models to study the environmental fate of those pollutants and the design of unit operations (e.g. adsorption) used for their removal require the knowledge of some key properties such as the diffusion coefficients in water. n-alcohols with perfluorinated carbon chains can be regarded as the most simple fluorinated surfactants, being suitable to be used as model substances that can make easier the molecular interpretation and the theoretical treatment of fluorinated surfactants in a systematic way. On the other hand, the smallest perfluorinated n-alcohols find applications in many fields, such as the pharmaceutical industry, polymer production and refrigerant technology as components of working fluids. We have recently reported intra-diffusion coefficients of 2,2,2-trifluoroethanol in water for dilute solutions as a function of composition and temperature, obtained both experimentally (NMR spin-echo) and by computer simulation (molecular dynamics) [3]. The results obtained by molecular dynamics closely reproduce the experimental ones, which has encouraged us to attempt predicting the dynamic properties of aqueous solutions of the higher fluorinated alcohols and other fluorinated surfactants. In this work, the intra-diffusion coefficients of 2,2,3,3,3-pentafluoropropan-1-ol, 2,2,3,3,4,4,4-heptafluorobutan-1-ol and 2,2,3,3,4,4,5,5,5-nonafluoropentan-1-ol in water and heavy water were measured experimentally by NMR spin-echo technique and compared with results obtained from computer simulation (molecular dynamics). The comparison that can be done between experimental and simulation results is used to test the theoretical models for this chemical family of substances and enriches the molecular interpretation of the results, which can be useful to anticipate trends for more complex fluorinated surfactants. [1] Buck, R. C.; Franklin, J.; Berger, U.; Conder, J. M.; Cousins, I. T.; de Voogt, P.; Jensen, A. A.; Kannan, K.; Mabury, S. A.; van Leeuwen, S., Integr. Environ. Assess. Manage 2011, 7, 513−541 [2] D’Hollander, W.; de Voogt, P.; De Coen, W.; Bervoets, L., Rev. Environ. Contam. Toxicol. 2010, 208, 179–215 [3] Pereira, L. A. M.; Martins, L. F. G.; Ascenso, J. R.; Morgado, P.; Prates Ramalho, J. P.; Filipe, E. J. M., submitted to publicatio

Uncovering the kiloparsec-scale stellar ring of NGC5128

We reveal the stellar light emerging from the kiloparsec-scale, ring-like structure of the NGC5128 (Centaurus A) galaxy in unprecedented detail. We use arcsecond-scale resolution near infrared images to create a "dust-free" view of the central region of the galaxy, which we then use to quantify the shape of the revealed structure. At the resolution of the data, the structure contains several hundreds of discreet, point-like or slightly elongated sources. Typical extinction corrected surface brightness of the structure is K_S = 16.5 mag/arcsec^2, and we estimate the total near infrared luminosity of the structure to be M = -21 mag. We use diffraction limited (FWHM resolution of ~ 0.1", or 1.6 pc) near infrared data taken with the NACO instrument on VLT to show that the structure decomposes into thousands of separate, mostly point-like sources. According to the tentative photometry, the most luminous sources have M_K = -12 mag, naming them red supergiants or relatively low-mass star clusters. We also discuss the large-scale geometry implied by the reddening signatures of dust in our near infrared images.Comment: 5 pages, 4 figures, accepted for publication in A&A Letters. A version with high resolution images can be downloaded from http://www.helsinki.fi/~jtkainul/CenALette

Ditopic Receptors Based on Dihomooxacalix[4]arenes Bearing Phenylurea Moieties With Electron-Withdrawing Groups for Anions and Organic Ion Pairs

Two bidentate dihomooxacalix[4]arene receptors bearing phenylurea moieties substituted with electron-withdrawing groups at the lower rim via a butyl spacer (CF3-Phurea 5b and NO2 Phurea 5c) were obtained in the cone conformation in solution, as shown by NMR. The X-ray crystal structure of 5b is reported. The binding affinity of these receptors toward several relevant anions was investigated by 1H NMR, UV-Vis absorption in different solvents, and fluorescence titrations. Compounds 5b and 5c were also tested as ditopic receptors for organic ion pairs, namely monoamine neurotransmitters and trace amine hydrochlorides by 1H NMR studies. The data showed that both receptors follow the same trend and, in comparison with the unsubstituted phenylurea 5a, they exhibit a significant enhancement on their host-guest properties, owing to the increased acidity of their urea NH protons. NO2-Phurea 5c is the best anion receptor, displaying the strongest complexation for F 12, closely followed by the oxoanions BzO 12, AcO 12, and HSO4-. Concerning ion pair recognition, both ditopic receptors presented an outstanding efficiency for the amine hydrochlorides, mainly 5c, with association constants higher than 109 M 122 in the case of phenylethylamine and tyramine

On the mobility of dialkyl adipates by PFGSE NMR, computer simulations and other property measurement methods

Encontro realizado em Alacalá de Henares (Madrid), de 22 a 25 de Setembro de 2014Dialkyl adipates are a class of esters materials used as components of lubricants and plasticizers. Diffusion of plasticizers in polymers is a complex process that is difficult to study [1]. As a contribution to understand this phenomenon, the self-diffusion coefficients of five dialkyl adipates (dimethyl, diethyl, dipropyl, dibuthyl and bis(2-ethylhexyl)) were measured by the PFGSTE method in the temperature range 20 to 60ºC. It was shown that these compounds follow the Stokes-Einstein equation [2]. In effect, the self-diffusion coefficients change linearly with T.η-1(η is the viscosity). The dependence of the activation energies for self-diffusion is discussed in terms of size and branching of the alkyl chains of the adipates. Molecular dynamics (MD) simulations were done for these sytems in order to predict the diffusion coefficients as a function of temperature [3]. Acknolwedgements: This work was supported by the Strategic Projects PEst-OE/QUI/UI0100/2011 and PEst-OE/QUI/ UI0100/2013, both funded by Fundação para a Ciência e a Tecnologia (FCT, Portugal). We thank also FCT for funding the NMR facility through Project RECI/QEQ-QIN/0189/2012. References: [1] Rahman M.; Brazel C. S., Prog. Polym. Sci. 2004, 29, 1223–1248. [2] Price W.S, NMR Studies of Translation Motion, Cambridge University Press, Cambridge, 2009. [3] Pereira, L. A. M.; Martins, L. F. G.; Ascenso, J. R; Morgado, P.; Ramalho, J. P. P.; Filipe, E. J. M., J. Chem. Eng. Data 2014, accepted for publication

Diffusion Coefficients of Fluorinated Surfactants in Water:

Intradiffusion coefficients of 2,2,2-trifluoroethanol in water have been measured by the pulsed field gradient (PFG)-NMR spin−echo technique as a function of temperature and composition on the dilute alcohol region. The measurements extend the range of compositions already studied in the literature and, for the first time, include the study of the temperature dependence. At the same time, intradiffusion coefficients of 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropan-1-ol, and 2,2,3,3,4,4,4-heptafluorobutan-1-ol in water were obtained by computer simulation (molecular dynamics) as a function of composition and temperature. The intradiffusion coefficients of 2,2,2-trifluoroethanol in water obtained by simulation agree with the experimental results, while those of 2,2,3,3,3- pentafluoropropan-1-ol and 2,2,3,3,4,4,4-heptafluorobutan-1-ol are the first estimation of this property for those systems. The molecular dynamics simulations were also used to calculate the intradiffusion coefficients of perfluorooctanesulfonic acid and perfluorooctanoic acid in water at infinite dilution as a function of temperature, which are very difficult to obtain experimentally because of the very low solubility of these substances. From the dependence of the intradiffusion coefficients on temperature, diffusion activation energies were estimated for all the solutes in water

Conventional vs. Microwave-or mechanically-assisted synthesis of dihomooxacalix[4]arene phthalimides: NMR, X-ray and photophysical analysis

Direct O-alkylation of p-tert-butyldihomooxacalix[4]arene (1) with N-(bromopropyl)-or N-(bromoethyl)phthalimides and K2 CO3 in acetonitrile was conducted under conventional heating (reflux) and using microwave irradiation and ball milling methodologies. The reactions afforded mono-and mainly distal di-substituted derivatives in the cone conformation, in a total of eight compounds. They were isolated by column chromatography, and their conformations and the substitution patterns were established by NMR spectroscopy (1 H,13 C, COSY and NOESY experiments). The X-ray structures of four dihomooxacalix[4]arene phthalimide derivatives (2a, 3a, 3b and 5a) are reported, as well as their photophysical properties. The microwave (MW)-assisted alkylations drastically reduced the reaction times (from days to less than 45 min) and produced higher yields of both 1,3-di-substituted phthalimides (3a and 6a) with higher selectivity. Ball milling did not reveal to be a good method for this kind of reaction

New OB star candidates in the Carina Arm around Westerlund 2 from VPHAS+

Date of Acceptance: 10/04/2015O and early B stars are at the apex of galactic ecology, but in the Milky Way, only a minority of them may yet have been identified. We present the results of a pilot study to select and parametrise OB star candidates in the Southern Galactic plane, down to a limiting magnitude of $g=20$. A 2 square-degree field capturing the Carina Arm around the young massive star cluster, Westerlund 2, is examined. The confirmed OB stars in this cluster are used to validate our identification method, based on selection from the $(u-g, g-r)$ diagram for the region. Our Markov Chain Monte Carlo fitting method combines VPHAS+ $u, g, r, i$ with published $J, H, K$ photometry in order to derive posterior probability distributions of the stellar parameters $\log(\rm T_{\rm eff})$ and distance modulus, together with the reddening parameters $A_0$ and $R_V$. The stellar parameters are sufficient to confirm OB status while the reddening parameters are determined to a precision of $\sigma(A_0)\sim0.09$ and $\sigma(R_V)\sim0.08$. There are 489 objects that fit well as new OB candidates, earlier than $\sim$B2. This total includes 74 probable massive O stars, 5 likely blue supergiants and 32 reddened subdwarfs. This increases the number of previously known and candidate OB stars in the region by nearly a factor of 10. Most of the new objects are likely to be at distances between 3 and 6 kpc. We have confirmed the results of previous studies that, at these longer distances, these sight lines require non-standard reddening laws with $3.5R_VPeer reviewe

The Age, Stellar Content and Star Formation Timescale of the B59 Dense Core

We have used moderate resolution, near-infrared spectra from the SpeX spectrograph on the NASA Infrared Telescope facility to characterize the stellar content of Barnard 59 (B59), the most active star-forming core in the Pipe Nebula. Measuring luminosity and temperature sensitive features in the spectra of 20 candidate YSOs, we identified likely background giant stars and measured each star's spectral type, extinction, and NIR continuum excess. We find that B59 is composed of late type (K4-M6) low-mass (0.9--0.1 M_sun) YSOs whose median stellar age is comparable to, if not slightly older than, that of YSOs within the Rho Oph, Taurus, and Chameleon star forming regions. Deriving absolute age estimates from pre-main sequence models computed by D'Antona et al., and accounting only for statistical uncertainties, we measure B59's median stellar age to be 2.6+/-0.8 Myrs. Including potential systematic effects increases the error budget for B59's median (DM98) stellar age to 2.6+4.1/-2.6 Myrs. We also find that the relative age orderings implied by pre-main sequence evolutionary tracks depend on the range of stellar masses sampled, as model isochrones possess significantly different mass dependencies. The maximum likelihood median stellar age we measure for B59, and the region's observed gas properties, suggest that the B59 dense core has been stable against global collapse for roughly 6 dynamical timescales, and is actively forming stars with a star formation efficiency per dynamical time of ~6%. This maximum likelihood value agrees well with recent star formation simulations that incorporate various forms of support against collapse, such as sub-critical magnetic fields, outflows, and radiative feedback from protostellar heating. [abridged]Comment: 20 pages, 12 figures, accepted for publication in the Astrophysical Journal; updated to amend acknowledgment