Molecularly-Imprinted Materials for Potentiometric Transduction: Application to the Antibiotic Enrofloxacin

Enrofloxacin (ENR) is an antimicrobial used both in humans and in food producing species. Its control is required in farmed species and their surroundings in order to reduce the prevalence of antibiotic resistant bacteria. Thus, a new biomimetic sensor enrofloxacin is presented. An artificial host was imprinted in specific polymers. These were dispersed in 2-nitrophenyloctyl ether and entrapped in a poly(vinyl chloride) matrix. The potentiometric sensors exhibited a near-Nernstian response. Slopes expressing mV/Δlog([ENR]/M) varied within 48–63. The detection limits ranged from 0.28 to 1.01 µg mL−1. Sensors were independent from the pH of test solutions within 4–7. Good selectivity was observed toward potassium, calcium, barium, magnesium, glycine, ascorbic acid, creatinine, norfloxacin, ciprofloxacin, and tetracycline. In flowing media, the biomimetic sensors presented good reproducibility (RSD of ± 0.7%), fast response, good sensitivity (47 mV/Δlog([ENR]/M), wide linear range (1.0 × 10−5–1.0 × 10−3 M), low detection limit (0.9 µg mL−1), and a stable baseline for a 5 × 10−2 M acetate buffer (pH 4.7) carrier. The sensors were used to analyze fish samples. The method offered the advantages of simplicity, accuracy, and automation feasibility. The sensing membrane may contribute to the development of small devices allowing in vivo measurements of enrofloxacin or parent-drugs.

Rhapsody in Fractional

This paper studies several topics related with the concept of “fractional” that are not directly related with Fractional Calculus, but can help the reader in pursuit new research directions. We introduce the concept of non-integer positional number systems, fractional sums, fractional powers of a square matrix, tolerant computing and FracSets, negative probabilities, fractional delay discrete-time linear systems, and fractional Fourier transform.

The potential of molecular imprinting as a biosensing devices for monitoring the CEA cancer biomarker

6th Graduate Student Symposium on Molecular Imprinting

A novel antibody-like material for breast cancer antigen CA15-3, used to track breast cancer by potentiometric transduction

This work presents the development of a low cost sensor device for the diagnosis of breast cancer in point-of-care, made with new synthetic biomimetic materials inside plasticized poly(vinyl chloride), PVC, membranes, for subsequent potentiometric detection. This concept was applied to target a conventional biomarker in breast cancer: Breast Cancer Antigen (CA15-3). The new biomimetic material was obtained by molecularly-imprinted technology. In this, a plastic antibody was obtained by polymerizing around the biomarker that acted as an obstacle to the growth of the polymeric matrix. The imprinted polymer was specifically synthetized by electropolymerization on an FTO conductive glass, by using cyclic voltammetry, including 40 cycles within -0.2 and 1.0 V. The reaction used for the polymerization included monomer (pyrrol, 5.0×10-3 mol/L) and protein (CA15-3, 100U/mL), all prepared in phosphate buffer saline (PBS), with a pH of 7.2 and 1% of ethylene glycol. The biomarker was removed from the imprinted sites by proteolytic action of proteinase K. The biomimetic material was employed in the construction of potentiometric sensors and tested with regard to its affinity and selectivity for binding CA15-3, by checking the analytical performance of the obtained electrodes. For this purpose, the biomimetic material was dispersed in plasticized PVC membranes, including or not a lipophilic ionic additive, and applied on a solid conductive support of graphite. The analytical behaviour was evaluated in buffer and in synthetic serum, with regard to linear range, limit of detection, repeatability, and reproducibility. This antibody-like material was tested in synthetic serum, and good results were obtained. The best devices were able to detect 5 times less CA15-3 than that required in clinical use. Selectivity assays were also performed, showing that the various serum components did not interfere with this biomarker. Overall, the potentiometric-based methods showed several advantages compared to other methods reported in the literature. The analytical process was simple, providing fast responses for a reduced amount of analyte, with low cost and feasible miniaturization. It also allowed the detection of a wide range of concentrations, diminishing the required efforts in previous sample pre-treating stages.

Host-Tailored Sensors for Carnitine Potentiometric Measurements based on Surface Molecular Imprinting

Graduate Student Symposium on Molecular Imprinting 2013, na Queen’s University, Belfast, United Kingdom, 15 a 17 de Agosto de 2013

Integer/fractional decomposition of the impulse response of fractional linear systems

The decomposition of a fractional linear system is discussed in this paper. It is shown that it can be decomposed into an integer order part, corresponding to possible existing poles, and a fractional part. The first and second parts are responsible for the short and long memory behaviors of the system, respectively, known as characteristic of fractional systems.

Discrete fractional order system vibrations

A theory of free vibrations of discrete fractional order (FO) systems with a finite number of degrees of freedom (dof) is developed. A FO system with a finite number of dof is defined by means of three matrices: mass inertia, system rigidity and FO elements. By adopting a matrix formulation, a mathematical description of FO discrete system free vibrations is determined in the form of coupled fractional order differential equations (FODE). The corresponding solutions in analytical form, for the special case of the matrix of FO properties elements, are determined and expressed as a polynomial series along time. For the eigen characteristic numbers, the system eigen main coordinates and the independent eigen FO modes are determined. A generalized function of visoelastic creep FO dissipation of energy and generalized forces of system with no ideal visoelastic creep FO dissipation of energy for generalized coordinates are formulated. Extended Lagrange FODE of second kind, for FO system dynamics, are also introduced. Two examples of FO chain systems are analyzed and the corresponding eigen characteristic numbers determined. It is shown that the oscillatory phenomena of a FO mechanical chain have analogies to electrical FO circuits. A FO electrical resistor is introduced and its constitutive voltage–current is formulated. Also a function of thermal energy FO dissipation of a FO electrical relation is discussed.

An Extension of Estimation of Domain of Attraction for Fractional Order Linear System Subject to Saturation Control

This paper employs the Lyapunov direct method for the stability analysis of fractional order linear systems subject to input saturation. A new stability condition based on saturation function is adopted for estimating the domain of attraction via ellipsoid approach. To further improve this estimation, the auxiliary feedback is also supported by the concept of stability region. The advantages of the proposed method are twofold: (1) it is straightforward to handle the problem both in analysis and design because of using Lyapunov method, (2) the estimation leads to less conservative results. A numerical example illustrates the feasibility of the proposed method.

QuEChERS: a sample preparation for extraction of carbaryl from rat feces

Carbamate compounds are an important group of cholinesterase inhibitors. There is a need for creating awareness regarding the risks of the inadequate carbamate use in the residential areas due to potential adverse human effects. Carbaryl is a commonly used pesticide worldwide. A simple, fast, and high throughput method was developed employing liquid chromatography with fluorescence detector to determine carbaryl residues in rat feces. The extraction was performed by using a rapid, easy, cheap, effective, reliable, and safe (QuEChERS) method, using acetonitrile as the extracting solvent. The parameters for the performance of the extraction method were optimized, such as ratio of mass of sample per volume of extraction solvent, QuEChERS content, and cleanup columns. Linear response was obtained for all calibration curves (solven and matrix-matched) over the established concentration range (5 500 mg/L) with a correlation coefficients higher than 0.999. The achieved recovery was 97.9% with relative standard deviation values of 1.1% (n D 4) at 167 mg/kg fortified concentration level and the limits of detection and quantification were 27.7 and 92.3 mg/kg respectively.

Matrix fractional systems

This paper addresses the matrix representation of dynamical systems in the perspective of fractional calculus. Fractional elements and fractional systems are interpreted under the light of the classical Cole–Cole, Davidson–Cole, and Havriliak–Negami heuristic models. Numerical simulations for an electrical circuit enlighten the results for matrix based models and high fractional orders. The conclusions clarify the distinction between fractional elements and fractional systems.

On the analysis of data emerging in non-linear and complex systemscomparison of two X-Ray prony spectra

New arguments proving that successive (repeated) measurements have a memory and actually remember each other are presented. The recognition of this peculiarity can change essentially the existing paradigm associated with conventional observation in behavior of different complex systems and lead towards the application of an intermediate model (IM). This IM can provide a very accurate fit of the measured data in terms of the Prony's decomposition. This decomposition, in turn, contains a small set of the fitting parameters relatively to the number of initial data points and allows comparing the measured data in cases where the “best fit” model based on some specific physical principles is absent. As an example, we consider two X-ray diffractometers (defined in paper as A- (“cheap”) and B- (“expensive”) that are used after their proper calibration for the measuring of the same substance (corundum a-Al2O3). The amplitude-frequency response (AFR) obtained in the frame of the Prony's decomposition can be used for comparison of the spectra recorded from (A) and (B) - X-ray diffractometers (XRDs) for calibration and other practical purposes. We prove also that the Fourier decomposition can be adapted to “ideal” experiment without memory while the Prony's decomposition corresponds to real measurement and can be fitted in the frame of the IM in this case. New statistical parameters describing the properties of experimental equipment (irrespective to their internal “filling”) are found. The suggested approach is rather general and can be used for calibration and comparison of different complex dynamical systems in practical purposes.

Electrochemical sensor for simultaneous determination of herbicide MCPA and its metabolite 4-chloro-2-methylphenol. Application to photodegradation environmental monitoring

The development and application of a polyaniline/carbon nanotube (CNT) cyclodextrin matrix (PANI-β-CD/MWCNT)-based electrochemical sensor for the quantitative determination of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) and its main transformation product 4-chloro-2-methylphenol in natural waters are described. A simple cyclic voltammetry-based electrochemical methodology, in phosphate buffer solution at pH 6.0, was used to develop a method to determine both MCPA and 4-chloro-2-methylphenol, without any previous extraction or derivatization steps. A linear concentration range (10 to 50 μmol L−1) and detection limits of 1.1 and 1.9 μmol L−1, respectively, were achieved using optimized cyclic voltammetric parameters. The proposed method was successfully applied to the determination of MCPA and 4-chloro-2-methylphenol in natural water samples with satisfactory recoveries (94 to 107 %) and in good agreement with the results obtained by an established high-performance liquid chromatography technique, no significant differences being found between the methods. Interferences from ionic species and other herbicides used for broad-leaf weed control were shown to be small. The newly developed methodology was also successfully applied to MCPA photodegradation environmental studies.

Analyzing Multiple Outcomes: Is it Really Worth the use of Multivariate Linear Regression?

In health related research it is common to have multiple outcomes of interest in a single study. These outcomes are often analysed separately, ignoring the correlation between them. One would expect that a multivariate approach would be a more efficient alternative to individual analyses of each outcome. Surprisingly, this is not always the case. In this article we discuss different settings of linear models and compare the multivariate and univariate approaches. We show that for linear regression models, the estimates of the regression parameters associated with covariates that are shared across the outcomes are the same for the multivariate and univariate models while for outcome-specific covariates the multivariate model performs better in terms of efficiency.

Kalman tracking linear predictor for vowel intelligibility enhancement on european portuguese HMM based speech synthesis

The recent developments on Hidden Markov Models (HMM) based speech synthesis showed that this is a promising technology fully capable of competing with other established techniques. However some issues still lack a solution. Several authors report an over-smoothing phenomenon on both time and frequencies which decreases naturalness and sometimes intelligibility. In this work we present a new vowel intelligibility enhancement algorithm that uses a discrete Kalman filter (DKF) for tracking frame based parameters. The inter-frame correlations are modelled by an autoregressive structure which provides an underlying time frame dependency and can improve time-frequency resolution. The system’s performance has been evaluated using objective and subjective tests and the proposed methodology has led to improved results.

Correlação entre a Extensão Linear do Tronco e o Alinhamento Segmentar do Membro Inferior Contralesional na Posição de Pé em Indivíduos Pós-AVE

O controlo postural (CP) do tronco é um pré-requisito para o movimento tendo como objetivo prevenir e minimizar as perturbações. Um CP adequado pressupõe estabilidade e orientação dos segmentos, sendo necessária uma orientação do tronco com componente de extensão linear para as atividades sentado e pé. Num acidente vascular encefálico (AVE), pode existir comprometimento do CP do tronco quer contralesional (CONTRA) como ipsilesional (IPSI). Neurofisiologicamente, parece haver uma projecção predominantemente ipsilateral para garantir um CP do tronco contralateralmente ao movimento, tornando-se importante perceber a correlação entre componentes do CP do tronco e o alinhamento do membro CONTRA. Contudo, atualmente são poucos os estudos direcionados para a o membro inferior (MI). Assim, uma vez que nesta população, assumir a posição de pé e realizar marcha constitui muitas vezes o seu principal objetivo, considerou-se relevante avaliar a correlação entre a extensão linear do tronco e o alinhamento segmentar do MI CONTRA na posição de pé. Participantes e Métodos: Estudo observacional, transversal, analítico com 11 indivíduos (idade média 70+10 anos, 54,5% homens). Como critérios de inclusão definiram-se AVE isquémico da artéria cerebral média, único e unilateral, em fase crónica. Recorrendo a um software de avaliação postural (SAPo) avaliou-se a extensão linear do tronco (alinhamento dos acrómios, alinhamento das espinhas ilíacas ântero-superiores (EIAS), ângulo formado entre os dois e o alinhamento vertical do tronco) e o alinhamento segmentar do MI (ângulo do joelho e ângulo entre o tronco e MI). Para a análise estatística inferencial utilizou-se o coeficiente de correlação de Pearson entre o ângulo dos acrómios e as EIAS, o alinhamento vertical do tronco e o alinhamento horizontal da pélvis IPSI com as variáveis de alinhamento do MI, para uma significância de 0,05. Resultados: Algumas correlações mostraram ser quase nulas (com valores entre -0,02 a 0,02) ou fracas como o alinhamento horizontal da pélvis IPSI com o ângulo do tronco e MI CONTRA (0,29 com p=0,39). O alinhamento do tronco e o ângulo do joelho apresentou moderada correlação (0,642), estatisticamente significativa (p=0,03). Conclusão: Os resultados deste estudo sugerem a existência de uma correlação positiva entre o alinhamento vertical do tronco e a extensão do joelho do MI CONTRA na posição de pé em indivíduos pós-AVE.