Removal of paracetamol on biomass-derived activated carbon: Modeling the fixed bed breakthrough curves using batch adsorption experiments

The remediation of paracetamol (PA), an emerging contaminant frequently found in wastewater treatment plants, has been studied in the low concentration range (0.3–10 mg L−1) using as adsorbent a biomass-derived activated carbon. PA uptake of up to 100 mg g−1 over the activated carbon has been obtained, with the adsorption isotherms being fairly explained by the Langmuir model. The application of Reichemberg and the Vermeulen equations to the batch kinetics experiments allowed estimating homogeneous and heterogeneous diffusion coefficients, reflecting the dependence of diffusion with the surface coverage of PA. A series of rapid small-scale column tests were carried out to determine the breakthrough curves under different operational conditions (temperature, PA concentration, flow rate, bed length). The suitability of the proposed adsorbent for the remediation of PA in fixed-bed adsorption was proven by the high PA adsorption capacity along with the fast adsorption and the reduced height of the mass transfer zone of the columns. We have demonstrated that, thanks to the use of the heterogeneous diffusion coefficient, the proposed mathematical approach for the numerical solution to the mass balance of the column provides a reliable description of the breakthrough profiles and the design parameters, being much more accurate than models based in the classical linear driving force.

Dysprosium transport in Nd-Fe-B pellets

The addition of heavy rare earth (RE) elements to Nd2Fe14B based magnets to form (Nd,Dy)2Fe14B is known to increase the coercivity and high temperature performance required for hybrid vehicle electric motors and other extreme temperature applications. Attempts to conserve heavy rare earth elements for high temperature (RE)2Fe14B based magnets have led to the development of a grain boundary diffusion process for bulk magnets. This process relies on transport of a heavy rare earth, such as Dy, into a bulk Nd2Fe14B magnet along pores, a low volume fraction of eutectic liquid along grain boundary grain triple junctions and grain boundaries. This enriches the grain surfaces in Dy through the thickness of the bulk magnet, leading to larger increases coercivity with a smaller Dy concentration than can be achieved with homogeneous alloys. Attempts to carry out the same process during sintering require significant control of Dy transport efficiency. The macroscopic transport of Dy in Nd2.7Fe14B1.4 based powder packs is studied using a 'layered' pellet, where Nd2.7Fe14B1.4powder is an interlayer and Dy source as a center layer. The sintering of this layered pellet provided evidence for very large effective diffusion lengths aided by Dy rich liquid flow through connected porosity. Approaches to controlling Dy transportation include decreasing the liquid phase transport capability of the powder pack by increasing the melting point of the Dy source and the decreasing amount of RE rich liquid in the powder packs. The solid-liquid reaction is studied in which melt spun Nd2.7Fe14B1.4 ribbons are PVD coated with Dy-Fe eutectic composition and then thermally treated. The resulting microstructure from the reaction between Dy-Fe eutectic coating and Nd2.7Fe14B1.4 ribbon is interpreted as support for a proposed dissolution/reprecipitation process between solid and liquid phases. The estimate the diffusion coefficient and the effective diffusion length of Dy sources in Nd2.7Fe14B1.4 layered pellets and melt spun ribbons were obtained from the calculation of Fick's second law combined with EDS results from the experiment. The results indicate that the effective diffusion coefficient of Dy in the layered pellets is higher than the diffusion in ribbons due to its higher porosity than ribbons.

Study of the absorption of organic compounds on biopolymers

This work has been conducted in order to determine the solubility and diffusion coefficients of different aromatic substances in two different grades of polylactic acid (PLA), Amorphous (PDLLA) and Crystalline (PLLA); in particular the focus is on the following terpenes: Linalool, α-Pinene, β-Citronellol and L-Linalool. Moreover, further analyses have been carried out with the aim to verify if the use of neat crystalline PLA, (PLLA), a chiral substrate, may lead to an enantioenrichment of absorbed species in order to use it as membrane in enantioselective processes. The other possible applications of PLA, which has aroused interest in carry out the above-mentioned work, concerns its use in food packaging. Therefore, it is interesting and also very important, to evaluate the barrier properties of PLA, focusing in particular on the transport and absorption of terpenes, by the packaging and, hence, by the PLA. PLA films/slabs of one-millimeter thickness and with square shape, were prepared through the Injection Molding process. On the resulting PLA films heat pretreatment processes of normalizing were then performed to enhance the properties of the material. In order to evaluate solubility and diffusion coefficient of the different penetrating species, the absorption kinetics of various terpenes, in the two different types of PLA, were determined by gravimetric methods. Subsequently, the absorbed liquid was extracted with methanol (MeOH), non- solvent for PLA, and the extract analyzed by the use of High Performance Liquid Chromatography (HPLC), in order to evaluate its possible enantiomeric excess. Moreover, PLA films used were subjected to differential scanning calorimetry (DSC) which allowed to measure the glass transition temperature (Tg) and to determine the degree of crystallinity of the polymer (Xc).

Diffusive models and chaos indicators for non-linear betatron motion in circular hadron accelerators

Understanding the complex dynamics of beam-halo formation and evolution in circular particle accelerators is crucial for the design of current and future rings, particularly those utilizing superconducting magnets such as the CERN Large Hadron Collider (LHC), its luminosity upgrade HL-LHC, and the proposed Future Circular Hadron Collider (FCC-hh). A recent diffusive framework, which describes the evolution of the beam distribution by means of a Fokker-Planck equation, with diffusion coefficient derived from the Nekhoroshev theorem, has been proposed to describe the long-term behaviour of beam dynamics and particle losses. In this thesis, we discuss the theoretical foundations of this framework, and propose the implementation of an original measurement protocol based on collimator scans in view of measuring the Nekhoroshev-like diffusive coefficient by means of beam loss data. The available LHC collimator scan data, unfortunately collected without the proposed measurement protocol, have been successfully analysed using the proposed framework. This approach is also applied to datasets from detailed measurements of the impact on the beam losses of so-called long-range beam-beam compensators also at the LHC. Furthermore, dynamic indicators have been studied as a tool for exploring the phase-space properties of realistic accelerator lattices in single-particle tracking simulations. By first examining the classification performance of known and new indicators in detecting the chaotic character of initial conditions for a modulated Hénon map and then applying this knowledge to study the properties of realistic accelerator lattices, we tried to identify a connection between the presence of chaotic regions in the phase space and Nekhoroshev-like diffusive behaviour, providing new tools to the accelerator physics community.

Variabilité intra/interobservateur du coefficient de diffusion apparente dans les lésions hépatiques malignes traitées

Objectifs : Le coefficient de diffusion apparente (ADC) est utilisé pour le suivi des lésions hépatiques malignes traitées. Cependant, l'ADC est généralement mesuré dans la lésion entière, alors que cela devrait être réalisé dans la zone la plus restreinte (ZLPR), cette dernière représentant potentiellement du résidu tumoral. Notre objectif était d'évaluer la variabilité inter/intraobservateur de l'ADC dans la tumeur entière et dans la ZLPR. Matériels et méthodes : Quarante patients traités par chimioembolisation ou radiofréquence ont été évalués. Après consensus, deux lecteurs ont indépendamment mesuré l'ADC de la lésion entière et de la ZLPR. Les mêmes mesures ont été répétées deux semaines plus tard. Le test de Spearman et la méthode de Bland-Altman ont été utilisées. Résultats : La corrélation interobservateur de l'ADC dans la lésion entière et dans la ZLPR était de 0,962 et de 0,884. La corrélation intraobservateur était de 0,992 et de 0,979, respectivement. Les limites de variabilité interobservateur (mm2/sec*10 - 3) étaient entre -0,25/+0,28 dans la lésion entière et entre -0,51/+0,46 dans la ZLPR. Les limites de variabilité intraobservateur étaient respectivement : -0,25/+0,24 et -0,43/+0,47. Conclusion : La corrélation inter/intraobservateur dans les mesures d'ADC est bonne. Toutefois, une variabilité limitée existe et doit être considérée lors de l'interprétation des valeurs d'ADC des tumeurs hépatiques.

Self and cross-velocity correlation functions and diffusion coefficients in liquids: a molecular dynamics study of binary mixtures of soft spheres

Molecular dynamics simulation is applied to the study of the diffusion properties in binary liquid mixtures made up of soft-sphere particles with different sizes and masses. Self- and distinct velocity correlation functions and related diffusion coefficients have been calculated. Special attention has been paid to the dynamic cross correlations which have been computed through recently introduced relative mean molecular velocity correlation functions which are independent on the reference frame. The differences between the distinct velocity correlations and diffusion coefficients in different reference frames (mass-fixed, number-fixed, and solvent-fixed) are discussed.

Predicting diffusion of innovations with self-organisation and machine learning

The main subject of this master's thesis was predicting diffusion of innovations. The prediction was done in a special case: product has been available in some countries, and based on its diffusion in those countries the prediction is done for other countries. The prediction was based on finding similar countries with Self-Organizing Map~(SOM), using parameters of countries. Parameters included various economical and social key figures. SOM was optimised for different products using two different methods: (a) by adding diffusion information of products to the country parameters, and (b) by weighting the country parameters based on their importance for the diffusion of different products. A novel method using Differential Evolution (DE) was developed to solve the latter, highly non-linear optimisation problem. Results were fairly good. The prediction method seems to be on a solid theoretical foundation. The results based on country data were good. Instead, optimisation for different products did not generally offer clear benefit, but in some cases the improvement was clearly noticeable. The weights found for the parameters of the countries with the developed SOM optimisation method were interesting, and most of them could be explained by properties of the products.

Attention through self-synchronisation in the spiking neuron stochastic diffusion network

The paper discusses ensemble behaviour in the Spiking Neuron Stochastic Diffusion Network, SNSDN, a novel network exploring biologically plausible information processing based on higher order temporal coding. SNSDN was proposed as an alternative solution to the binding problem [1]. SNSDN operation resembles Stochastic Diffusin on Search, SDS, a non-deterministic search algorithm able to rapidly locate the best instantiation of a target pattern within a noisy search space ([3], [5]). In SNSDN, relevant information is encoded in the length of interspike intervals. Although every neuron operates in its own time, ‘attention’ to a pattern in the search space results in self-synchronised activity of a large population of neurons. When multiple patterns are present in the search space, ‘switching of at- tention’ results in a change of the synchronous activity. The qualitative effect of attention on the synchronicity of spiking behaviour in both time and frequency domain will be discussed.

Transdentinal diffusion and cytotoxicity of self-etching adhesive systems

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Integrable NLS equation with time-dependent nonlinear coefficient and self-similar attractive BEC

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Validity and reliability of self-reported weight and height measures for the diagnoses of adolescent's nutritional status

OBJETIVO: Avaliar a validade do peso, estatura e Índice de Massa Corporal (IMC) referidos e sua confiabilidade para o diagnóstico do estado nutricional de adolescentes de Piracicaba. MÉTODOS: Participaram do estudo 360 adolescentes de ambos os sexos, de escolas públicas de Piracicaba, com idade entre 10 e 15 anos. Os adolescentes auto-relataram seu peso e estatura, sendo esses valores obtidos por medidas diretas, logo em seguida, pelos entrevistadores. A validade do IMC referido foi calculada segundo índices de sensibilidade, especificidade e valor preditivo positivo (VPP). Avaliou-se a concordância entre as categorias de IMC obtido por meio das medidas referidas e aferidas a partir do coeficiente kappa ponderado, coeficiente de correlação de Lin. e gráficos de Bland e Altman e Lin. RESULTADOS: Verificou-se que tanto os meninos quanto as meninas subestimaram o peso (-1,0 meninas e meninos) e a estatura (meninas -1,2 e meninos -0,8) (p < 0,001). Os valores de IMC aferidos e referidos apresentaram uma concordância moderada. A sensibilidade do IMC referido para classificar os indivíduos obesos foi maior para os meninos (87,5%), enquanto a especificidade foi maior para as meninas (92,7%). O VPP foi elevado somente para a classificação da eutrofia. CONCLUSÕES: As medidas referidas de peso e estatura de adolescentes não representam medidas válidas e, portanto, não devem ser usadas em substituição aos valores mensurados. Além disso, verificou-se que 10% dos meninos obesos e 40% das meninas obesas poderiam permanecer não identificados utilizando-se as medidas auto-referidas, confirmando a baixa validade das medidas auto-referidas.

Electrochemical and spectroscopic characterization of screen-printed gold-based electrodes modified with self-assembled monolayers and Tc85 protein

This work investigates the formation of self-assembled monolayers (SAMs) of cystamine and cystamine-glutaraldehyde on a screen-printed electrode, and the immobilization of the Tc85 protein (from Trypanosoma cruzi) on these monolayers. The methods used included infrared techniques, cyclic voltammetry, and electrochemical impedance spectroscopy. The electrochemical studies were performed at pH 6.9 in 0.1 mol L(-1) phosphate buffer solution containing Fe(CN)(6)(-3/-4) redox species. The surface coverage (0) of the electrode was 0.10 (cystamine), 0.35 (cystamine-glutaraldehyde) and 0.84 (Tc85). Interpretation of electrochemical impedance spectroscopy results was based on a charge-transfer reaction involving Fe(CN)(6)(-3/-4) species at high frequencies, followed by a diffusion through the monolayers at lower frequencies. Estimates of the electrode surface coverage, active site radius, and distance between two adjacent sites assumed that charge transfer occurred at the active sites, and that there was a planar diffusion of redox species to these sites. (C) 2009 Elsevier B.V. All rights reserved.

Test–retest repeatability of self-reported environmental exposures in Parkinson’s disease cases and healthy controls

There is substantial disagreement among published epidemiological studies regarding environmental risk factors for Parkinson’s disease (PD). Differences in the quality of measurement of environmental exposures may contribute to this variation. The current study examined the test–retest repeatability of self-report data on risk factors for PD obtained from a series of 32 PD cases recruited from neurology clinics and 29 healthy sex-, age-and residential suburb-matched controls. Exposure data were collected in face-to-face interviews using a structured questionnaire derived from previous epidemiological studies. High repeatability was demonstrated for ‘lifestyle’ exposures, such as smoking and coffee/tea consumption (kappas 0.70–1.00). Environmental exposures that involved some action by the person, such as pesticide application and use of solvents and metals, also showed high repeatability (kappas>0.78). Lower repeatability was seen for rural residency and bore water consumption (kappa 0.39–0.74). In general, we found that case and control participants provided similar rates of incongruent and missing responses for categorical and continuous occupational, domestic, lifestyle and medical exposures.

Two-wave-mixing induced self-focusing in an active photorefractive oscillator

We derive a nonlinear wave equation for a signal beam which is coupled to a pump beam by two-wave-mixing in a photorefractive crystal. This equation describes self-focusing of the signal beam. We compare two-wave-mixing induced spatial self-focusing of single-pass experiments in a diffusion-type photorefractive crystal and of a photorefractive oscillator using the same crystal. We observe that the nonlinear refractive index change in the oscillator is decreased while increasing resonator losses.