Improving IRT parameter estimates with small sample sizes: Evaluating the efficacy of a new data augmentation technique

The 3PL model is a flexible and widely used tool in assessment. However, it suffers from limitations due to its need for large sample sizes. This study introduces and evaluates the efficacy of a new sample size augmentation technique called Duplicate, Erase, and Replace (DupER) Augmentation through a simulation study. Data are augmented using several variations of DupER Augmentation (based on different imputation methodologies, deletion rates, and duplication rates), analyzed in BILOG-MG 3, and results are compared to those obtained from analyzing the raw data. Additional manipulated variables include test length and sample size. Estimates are compared using seven different evaluative criteria. Results are mixed and inconclusive. DupER augmented data tend to result in larger root mean squared errors (RMSEs) and lower correlations between estimates and parameters for both item and ability parameters. However, some DupER variations produce estimates that are much less biased than those obtained from the raw data alone. For one DupER variation, it was found that DupER produced better results for low-ability simulees and worse results for those with high abilities. Findings, limitations, and recommendations for future studies are discussed. Specific recommendations for future studies include the application of Duper Augmentation (1) to empirical data, (2) with additional IRT models, and (3) the analysis of the efficacy of the procedure for different item and ability parameter distributions.

Quantification of terbinafine in pharmaceutical tablets using capillary electrophoresis with contactless conductivity detection and batch injection analysis with amperometric detection

Terbinafine hydrochloride (TerbHCl) is an allylamine derivative with fungicidal action, especially against dermatophytes. Different analytical methods have been reported for quantifying TerbHCl in different samples. These procedures require time-consuming sample preparation or expensive instrumentation. In this paper, electrochemical methods involving capillary electrophoresis with contactless conductivity detection, and amperometry associated with batch injection analysis, are described for the determination of TerbHCl in pharmaceutical products. In the capillary electrophoresis experiments, terbinafine was protonated and analyzed in the cationic form in less than 1 min. A linear range from 1.46 to 36.4 mu g mL(-1) in acetate buffer solution and a detection limit of 0.11 mu g mL(-1) were achieved. In the amperometric studies, terbinafine was oxidized at +0.85 V with high throughput (225 injection h(-1)) and good linear range (10-100 mu mol L-1). It was also possible to determine the antifungal agent using simultaneous conductometric and potentiometric titrations in the presence of 5% ethanol. The electrochemical methods were applied to the quantification of TerbHCl in different tablet samples; the results were comparable with values indicated by the manufacturer and those found using titrimetry according to the Pharmacopoeia. The electrochemical methods are simple, rapid and an appropriate alternative for quantifying this drug in real samples. (C) 2012 Elsevier B.V. All rights reserved.

Spectral Induced Polarization (SIP) signatures of clayey soils containing toluene

We performed laboratory experiments to investigate the sensitivity of the Spectral Induced Polarization (SIP) method to toluene contamination in clayey soils. We used mixtures of quartzitic sand and montmorillonite as soil samples, artificially contaminated with varying amounts of toluene. Care was taken to quantify the experimental uncertainty resulting from packing since such effects must be quantified if variations in SIP signatures between samples are to be reliably interpreted in terms of the effects of hydrocarbon concentration. The SIP response of all samples following addition of toluene was monitored for a period of 40 days following sample preparation. Stepwise regression was used to examine the statistical significance of correlations between (i) clay content and (ii) toluene concentration and SIP parameters. Both single-frequency real and imaginary conductivity measurements, along with the integral chargeability, normalized chargeability, DC conductivity and time constant obtained from a Debye decomposition fitting, were examined in this regression analysis. The SIP measurements show a clear time dependence following sample preparation, indicating that samples containing toluene may take significant time to reach an equilibrium electrical response. SIP measurements are significantly related to toluene content shortly after sample preparation, when the expected dependence of SIP on clay concentration is apparently suppressed. However, for the state of electrical equilibrium after 40 days (interpreted to indicate surface chemistry at equilibrium) there is no significant relation between SIP measurements and toluene content; instead SIP measurements are then significantly correlated with clay concentration. The total chargeability, normalized chargeability and relaxation time obtained from the Debye decomposition show no correlation with toluene content, indicating that this procedure, which likely integrates over multiple mechanisms, may not be suitable for understanding relationships between SIP and hydrocarbon contamination. We find only small low-frequency polarization signals observed in relation to toluene concentration (2 mrad at 0.01 Hz), which initially decreases the interfacial polarization. Unlike earlier works, our results do not support the use of the SIP method as a tool for monitoring toluene contamination in clay soils.

Hybrid Water Demand Forecasting Model Associating Artificial Neural Network with Fourier Series

This paper addressed the problem of water-demand forecasting for real-time operation of water supply systems. The present study was conducted to identify the best fit model using hourly consumption data from the water supply system of Araraquara, Sa approximate to o Paulo, Brazil. Artificial neural networks (ANNs) were used in view of their enhanced capability to match or even improve on the regression model forecasts. The ANNs used were the multilayer perceptron with the back-propagation algorithm (MLP-BP), the dynamic neural network (DAN2), and two hybrid ANNs. The hybrid models used the error produced by the Fourier series forecasting as input to the MLP-BP and DAN2, called ANN-H and DAN2-H, respectively. The tested inputs for the neural network were selected literature and correlation analysis. The results from the hybrid models were promising, DAN2 performing better than the tested MLP-BP models. DAN2-H, identified as the best model, produced a mean absolute error (MAE) of 3.3 L/s and 2.8 L/s for training and test set, respectively, for the prediction of the next hour, which represented about 12% of the average consumption. The best forecasting model for the next 24 hours was again DAN2-H, which outperformed other compared models, and produced a MAE of 3.1 L/s and 3.0 L/s for training and test set respectively, which represented about 12% of average consumption. DOI: 10.1061/(ASCE)WR.1943-5452.0000177. (C) 2012 American Society of Civil Engineers.

The importance of landscape structure for seed dispersal in rain forest fragments

Questions What are the main features of the seed rain in a fragmented Atlantic forest landscape? Can seed rain species attributes (life form, dispersal mode, successional status) relate to the spatial arrangement (size and number of fragments, edge density and presence of corridor) of forest fragments in the landscape? How does the rain forest landscape structure affect the seed rain? Location Atlantic rainforest, Sao Paulo State, Southeastern Brazil. Methods Seed rain samples were collected monthly throughout 1yr, counted, identified and classified according to species dispersal mode, successional status and life form. Seed rain composition was compared with woody species near the seed traps. Relationships between seed rain composition and landscape spatial arrangement (fragment area, presence of corridor, number of fragments in the surroundings, proximity of fragments, and edge density) were tested using canonical correspondence analysis (CCA). Results We collected 20142 seeds belonging to 115 taxa, most of them early successional and anemochorous trees. In general, the seed rain had a species composition distinct from that of the nearby forest tree community. Small isolated fragments contained more seeds, mainly of anemochorous, epiphytic and early-successional species; large fragments showed higher association with zoochorous and late-successional species compared to small fragments. The CCA significantly distinguished the species dispersal mode according to fragment size and isolation, anemochorous species being associated to small and isolated fragments, and zoochorous species to larger areas and fragment aggregation. Nevertheless, a gradient driven by proximity (PROX) and edge density (ED) segregated lianas (in the positive extremity), early successional and epiphyte species (in the negative end); large fragments were positively associated to PROX and ED. Conclusions The results highlight the importance of the size and spatial arrangement of forest patches to promote habitat connectivity and improve the flux of animal-dispersed seeds. Landscape structure controls seed fluxes and affects plant dispersal capacity, potentially influencing the composition and structure of forest fragments. The seed rain composition may be used to assess the effects of landscape spatial structure on plant assemblages, and provide relevant information for biodiversity conservation.

Disposable polyester-toner electrophoresis microchips for DNA analysis

Microchip electrophoresis has become a powerful tool for DNA separation, offering all of the advantages typically associated with miniaturized techniques: high speed, high resolution, ease of automation, and great versatility for both routine and research applications. Various substrate materials have been used to produce microchips for DNA separations, including conventional (glass, silicon, and quartz) and alternative (polymers) platforms. In this study, we perform DNA separation in a simple and low-cost polyester-toner (PeT)-based electrophoresis microchip. PeT devices were fabricated by a direct-printing process using a 600 dpi-resolution laser printer. DNA separations were performed on PeT chip with channels filled with polymer solutions (0.5% m/v hydroxyethylcellulose or hydroxypropylcellulose) at electric fields ranging from 100 to 300Vcm(-1). Separation of DNA fragments between 100 and 1000 bp, with good correlation of the size of DNA fragments and mobility, was achieved in this system. Although the mobility increased with increasing electric field, separations showed the same profile regardless of the electric field. The system provided good separation efficiency (215 000 plates per m for the 500 bp fragment) and the separation was completed in 4 min for 1000 bp fragment ladder. The cost of a given chip is approximately $0.15 and it takes less than 10 minutes to prepare a single device.

Different protocols to produce artificial dentine carious lesions in vitro and in situ: hardness and mineral content correlation

This study compared dentine demineralization induced by in vitro and in situ models, and correlated dentine surface hardness (SH), cross-sectional hardness (CSH) and mineral content by transverse microradiography (TMR). Bovine dentine specimens (n = 15/group) were demineralized in vitro with the following: MC gel (6% carboxymethylcellulose gel and 0.1 m lactic acid, pH 5.0, 14 days); buffer I (0.05 m acetic acid solution with calcium, phosphate and fluoride, pH 4.5, 7 days); buffer II (0.05 m acetic acid solution with calcium and phosphate, pH 5.0, 7 days), and TEMDP (0.05 m lactic acid with calcium, phosphate and tetraethyl methyl diphosphonate, pH 5.0, 7 days). In an in situ study, 11 volunteers wore palatal appliances containing 2 bovine dentine specimens, protected with a plastic mesh to allow biofilm development. The volunteers dripped a 20% sucrose solution on each specimen 4 times a day for 14 days. In vitro and in situ lesions were analyzed using TMR and statistically compared by ANOVA. TMR and CSH/SH were submitted to regression and correlation analysis (p < 0.05). The in situ model produced a deep lesion with a high R value, but with a thin surface layer. Regarding the in vitro models, MC gel produced only a shallow lesion, while buffers I and II as well as TEMDP induced a pronounced subsurface lesion with deep demineralization. The relationship between CSH and TMR was weak and not linear. The artificial dentine carious lesions induced by the different models differed significantly, which in turn might influence further de- and remineralization processes. Hardness analysis should not be interpreted with respect to dentine mineral loss

Her2p molecular modeling, mutant analysis and intramitochondrial localization

Bacterial GatCAB amidotransferases are responsible for the transamidation of mischarged glutamyl-tRNA(Gln) into glutaminyl-tRNA(Gln). Mitochondria matrix also has a multienzymatic complex necessary for the transamidation of glutamyl-tRNA(Gln). Gtf1p, Her2p and Pet112p are the constituents of mitochondrial GatFAB amidotransferase complex. Her2p is subunit A of GatFAB complex, while Gtf1p is subunit F, a connector protein between Pet112p (subunit B) and Her2p. Here we evaluate through molecular modeling and amino acid correlation analysis the HER2 protein family. Localization studies indicated that Her2p is predominantly localized in the mitochondrial outer membrane, but it is also located in the mitochondrial matrix where together with Pet112p and Gtf1p constitutes the GatFAB complex. Finally, HER2 random mutagenesis unveiled important residues that provide thermo stability for the complex and are differently suppressed by overexpression of GTF1 or PET112. For instance, her2/ts11 mutant showed its fermentative growth impaired, and poorly rescued by GTF1 indicating that Her2p unknown function in the mitochondria outer membrane affects cell viability.

Inhibitors of Trypanosoma brucei trypanothione reductase: comparative molecular field analysis modeling and structural basis for selective inhibition

Background: Sleeping sickness is a major cause of death in Africa. Since no secure treatment is available, the development of novel therapeutic agents is urgent. In this context, the enzyme trypanothione reductase (TR) is a prominent molecular target that has been investigated in drug design for sleeping sickness. Results: In this study, comparative molecular field analysis models were generated for a series of Trypanosoma brucei TR inhibitors. Statistically significant results were obtained and the models were applied to predict the activity of external test sets, with good correlation between predicted and experimental results. We have also investigated the structural requirements for the selective inhibition of the parasite's enzyme over the human glutathione reductase. Conclusion: The quantitative structure-activity relationship models provided valuable information regarding the essential molecular requirements for the inhibitory activity upon the target protein, providing important insights into the design of more potent and selective TR inhibitors.

Scherverhalten kolloidaler Lagenphasen in Rohrströmungen

Kolloidale Suspensionen aus identischen kugelförmigen, geladenen Partikeln in wässrigen Medien stellen ein ideales Modellsystem zur Untersuchung des Gleichgewichtsverhaltens, aber auch des Nicht-Gleichgewichtsverhaltens Weicher Materie dar. So bilden derartige Systeme bei hinreichend starker und langreichweitiger elektrostatischer Repulsion fluid und kristallin geordnete Strukturen aus, die wegen der weitreichenden Analogie zu atomar kondensierter Materie als kolloidale Fluide und Kristalle bezeichnet werden. Von großem Vorteil ist dabei die Möglichkeit zur kontrollierten Einstellung der Wechselwirkung und die gute optische Zugänglichkeit für Mikroskopie und Lichtstreuung sowie die Weichheit der Materialien, aufgrund derer sich auch Zustände fernab des mechanischen Gleichgewichts gezielt präparieren lassen. Themenstellung der vorliegenden Arbeit ist die Untersuchung des Phasenverhaltens und der Fließmechanismen kolloidaler Kristalle in einer Rohrströmung. Im ersten Teil der Arbeit wird gezeigt, dass beim Fluss durch eine zylindrische Röhre Mehrphasenkoexistenz auftritt, wobei ein polykristalliner Kern von einer isotropen Scherschmelze umgeben ist. Zusätzlich treten an der Grenze zwischen diesen Phasen und an der Rohrwand Phasen hexagonal geordneter übereinander hinweggleitender Lagen auf. Der Vergleich zwischen auf der Basis der Navier-Stokes-Gleichung theoretisch berechneten und gemessenen Geschwindigkeitsprofilen zeigt, dass jede dieser Phasen für sich Newtonsches Fließverhalten aufweist. Die Gesamtviskosität ist hingegen durch die mit dem Durchsatz veränderliche Phasenzusammensetzung Nicht-Newtonsch. Damit gelang es, die erstmalig von Würth beschriebene Scherverdünnung auf eine Veränderung der Phasenzusammensetzung zurückzuführen. Im zweiten Teil der Arbeit wurde erstmals das Fließverhalten der Lagenphasen mittels Lichtstreuung und Korrelationsanalyse untersucht. Dafür wurde ein im Prinzip einfacher, aber leistungsstarker Aufbau realisiert, der es erlaubt, die zeitliche Veränderung der Bragg-Reflexe der Lagenphase in radialer und azimutaler Richtung zu verfolgen und mittels Fourieranalyse zu analysieren. In Abhängigkeit vom Durchsatz geht die zunächst rastend gleitende Lagenphase in eine frei gleitende Lagenphase über, wobei charakteristische Veränderungen der Spektren sowie der Korrelationsfunktionen auftreten, die detailliert diskutiert werden. Der Übergang im Gleitmechanismus ist mit einem Verlust der Autokorrelation der Rotationskomponente der periodischen Intra-Lagenverzerrung verbunden, während die Kompressionskomponente erhalten bleibt. Bei hohen Durchflüssen lassen die Reflexbewegungen auf das Auftreten einer Eigenschwingung der frei gleitenden Lagen schließen. Diese Schwingung lässt sich als Rotationsbewegung, gekoppelt mit einer transversalen Auslenkung in Vortexrichtung, beschreiben. Die Ergebnisse erlauben eine detaillierte Diskussion von verschiedenen Modellvorstellungen anderer Autoren.

Characterization of a dual-energy X-ray absorptiometry system for soft tissues assessment and their correlations with metabolic state

Il crescente utilizzo di sistemi di analisi high-throughput per lo studio dello stato fisiologico e metabolico del corpo, ha evidenziato che una corretta alimentazione e una buona forma fisica siano fattori chiave per la salute. L'aumento dell'età media della popolazione evidenzia l'importanza delle strategie di contrasto delle patologie legate all'invecchiamento. Una dieta sana è il primo mezzo di prevenzione per molte patologie, pertanto capire come il cibo influisce sul corpo umano è di fondamentale importanza. In questo lavoro di tesi abbiamo affrontato la caratterizzazione dei sistemi di imaging radiografico Dual-energy X-ray Absorptiometry (DXA). Dopo aver stabilito una metodologia adatta per l'elaborazione di dati DXA su un gruppo di soggetti sani non obesi, la PCA ha evidenziato alcune proprietà emergenti dall'interpretazione delle componenti principali in termini delle variabili di composizione corporea restituite dalla DXA. Le prime componenti sono associabili ad indici macroscopici di descrizione corporea (come BMI e WHR). Queste componenti sono sorprendentemente stabili al variare dello status dei soggetti in età, sesso e nazionalità. Dati di analisi metabolica, ottenuti tramite Magnetic Resonance Spectroscopy (MRS) su campioni di urina, sono disponibili per circa mille anziani (provenienti da cinque paesi europei) di età compresa tra i 65 ed i 79 anni, non affetti da patologie gravi. I dati di composizione corporea sono altresì presenti per questi soggetti. L'algoritmo di Non-negative Matrix Factorization (NMF) è stato utilizzato per esprimere gli spettri MRS come combinazione di fattori di base interpretabili come singoli metaboliti. I fattori trovati sono stabili, quindi spettri metabolici di soggetti sono composti dallo stesso pattern di metaboliti indipendentemente dalla nazionalità. Attraverso un'analisi a singolo cieco sono stati trovati alti valori di correlazione tra le variabili di composizione corporea e lo stato metabolico dei soggetti. Ciò suggerisce la possibilità di derivare la composizione corporea dei soggetti a partire dal loro stato metabolico.

Bonding of restorative materials to dentin with various luting agents

The aim was to compare eight types of luting agents when used to bond six indirect, laboratory restorative materials to dentin. Cylinders of the six restorative materials (Esteticor Avenir [gold alloy], Tritan [titanium], NobelRondo [feldspathic porcelain], Finesse All-Ceramic [leucite-glass ceramic], Lava [zirconia], and Sinfony [resin composite]) were ground and air-abraded. Cylinders of feldspathic porcelain and glass ceramic were additionally etched with hydrofluoric acid and were silane-treated. The cylinders were luted to ground human dentin with eight luting agents (DeTrey Zinc [zinc phosphate cement], Fuji I [conventional glass ionomer cement], Fuji Plus [resin-modified glass ionomer cement], Variolink II [conventional etch-and-rinse resin cement], Panavia F2.0 and Multilink [self-etch resin cements], and RelyX Unicem Aplicap and Maxcem [self-adhesive resin cements]). After water storage at 37°C for one week, the shear bond strength of the specimens (n=8/group) was measured, and the fracture mode was stereomicroscopically examined. Bond strength data were analyzed with two-factorial analysis of variance (ANOVA) followed by Newman-Keuls' Multiple Range Test (?=0.05). Both the restorative material and the luting agent had a significant effect on bond strength, and significant interaction was noted between the two variables. Zinc phosphate cement and glass ionomer cements produced the lowest bond strengths, whereas the highest bond strengths were found with the two self-etch and one of the self-adhesive resin cements. Generally, the fracture mode varied markedly with the restorative material. The luting agents had a bigger influence on bond strength between restorative materials and dentin than was seen with the restorative material.

Determination of free and total valproic acid in human plasma by capillary electrophoresis with contactless conductivity detection

A new approach for the determination of free and total valproic acid in small samples of 140 μL human plasma based on capillary electrophoresis with contactless conductivity detection is proposed. A dispersive liquid-liquid microextraction technique was employed in order to remove biological matrices prior to instrumental analysis. The free valproic acid was determined by isolating free valproic acid from protein-bound valproic acid by ultrafiltration under centrifugation of 100 μL sample. The filtrate was acidified to turn valproic acid into its protonated neutral form and then extracted. The determination of total valproic acid was carried out by acidifying 40 μL untreated plasma to release the protein-bound valproic acid prior to extraction. A solution consisting of 10 mM histidine, 10 mM 3-(N-morpholino)propanesulfonic acid and 10 μM hexadecyltrimethylammonium bromide of pH 6.5 was used as background electrolyte for the electrophoretic separation. The method showed good linearity in the range of 0.4-300 μg/mL with a correlation coefficient of 0.9996. The limit of detection was 0.08 μg/mL, and the reproducibility of the peak area was excellent (RSD=0.7-3.5%, n=3, for the concentration range from 1 to 150 μg/mL). The results for the free and total valproic acid concentration in human plasma were found to be comparable to those obtained with a standard immunoassay. The corresponding correlation coefficients were 0.9847 for free and 0.9521 for total valproic acid.

Cardiac transplantation with hearts from donors after circulatory declaration of death: haemodynamic and biochemical parameters at procurement predict recovery following cardioplegic storage in a rat model

OBJECTIVES: Donation after circulatory declaration of death (DCDD) could significantly improve the number of cardiac grafts for transplantation. Graft evaluation is particularly important in the setting of DCDD given that conditions of cardio-circulatory arrest and warm ischaemia differ, leading to variable tissue injury. The aim of this study was to identify, at the time of heart procurement, means to predict contractile recovery following cardioplegic storage and reperfusion using an isolated rat heart model. Identification of reliable approaches to evaluate cardiac grafts is key in the development of protocols for heart transplantation with DCDD. METHODS: Hearts isolated from anaesthetized male Wistar rats (n = 34) were exposed to various perfusion protocols. To simulate DCDD conditions, rats were exsanguinated and maintained at 37°C for 15-25 min (warm ischaemia). Isolated hearts were perfused with modified Krebs-Henseleit buffer for 10 min (unloaded), arrested with cardioplegia, stored for 3 h at 4°C and then reperfused for 120 min (unloaded for 60 min, then loaded for 60 min). Left ventricular (LV) function was assessed using an intraventricular micro-tip pressure catheter. Statistical significance was determined using the non-parametric Spearman rho correlation analysis. RESULTS: After 120 min of reperfusion, recovery of LV work measured as developed pressure (DP)-heart rate (HR) product ranged from 0 to 15 ± 6.1 mmHg beats min(-1) 10(-3) following warm ischaemia of 15-25 min. Several haemodynamic parameters measured during early, unloaded perfusion at the time of heart procurement, including HR and the peak systolic pressure-HR product, correlated significantly with contractile recovery after cardioplegic storage and 120 min of reperfusion (P < 0.001). Coronary flow, oxygen consumption and lactate dehydrogenase release also correlated significantly with contractile recovery following cardioplegic storage and 120 min of reperfusion (P < 0.05). CONCLUSIONS: Haemodynamic and biochemical parameters measured at the time of organ procurement could serve as predictive indicators of contractile recovery. We believe that evaluation of graft suitability is feasible prior to transplantation with DCDD, and may, consequently, increase donor heart availability.

Effect of acute hypoxia on maximal oxygen uptake and maximal performance during leg and upper-body exercise in Nordic combined skiers

We examined the effect of normobaric hypoxia (3200 m) on maximal oxygen uptake (VO2max) and maximal power output (Pmax) during leg and upper-body exercise to identify functional and structural correlates of the variability in the decrement of VO2max (DeltaVO2max) and of maximal power output (DeltaPmax). Seven well trained male Nordic combined skiers performed incremental exercise tests to exhaustion on a cycle ergometer (leg exercise) and on a custom built doublepoling ergometer for cross-country skiing (upper-body exercise). Tests were carried out in normoxia (560 m) and normobaric hypoxia (3200 m); biopsies were taken from m. deltoideus. DeltaVO2max was not significantly different between leg (-9.1+/-4.9%) and upper-body exercise (-7.9+/-5.8%). By contrast, Pmax was significantly more reduced during leg exercise (-17.3+/-3.3%) than during upper-body exercise (-9.6+/-6.4%, p<0.05). Correlation analysis did not reveal any significant relationship between leg and upper-body exercise neither for DeltaVO2max nor for DeltaPmax. Furthermore, no relationship was observed between individual DeltaVO2max and DeltaPmax. Analysis of structural data of m. deltoideus revealed a significant correlation between capillary density and DeltaPmax (R=-0.80, p=0.03), as well as between volume density of mitochondria and DeltaPmax (R=-0.75, p=0.05). In conclusion, it seems that VO2max and Pmax are differently affected by hypoxia. The ability to tolerate hypoxia is a characteristic of the individual depending in part on the exercise mode. We present evidence that athletes with a high capillarity and a high muscular oxidative capacity are more sensitive to hypoxia.