A green flow-based procedure for fluorimetric determination of acid-dissociable cyanide in natural waters exploiting multicommutation

A flow system designed with solenoid valves is proposed for determination of weak acid dissociable cyanide, based on the reaction with o-phthalaldehyde (OPA) and glycine yielding a highly fluorescent isoindole derivative. The proposed procedure minimizes the main drawbacks related to the reference batch procedure, based on reaction with barbituric acid and pyridine followed by spectrophotometric detection, i.e., use of toxic reagents, high reagent consumption and waste generation, low sampling rate, and poor sensitivity. Retention of the sample zone was exploited to increase the conversion rate of the analyte with minimized sample dispersion. Linear response (r=0.999) was observed for cyanide concentrations in the range 1-200 mu g L(-1), with a detection limit (99.7% confidence level) of 0.5 mu g L(-1)(19 nmol L(-1)). The sampling rate and coefficient of variation (n=10) were estimated as 22 measurements per hour and 1.4%, respectively. The results of determination of weak acid dissociable cyanide in natural water samples were in agreement with those achieved by the batch reference procedure at the 95% confidence level. Additionally to the improvement in the analytical features in comparison with those of the flow system with continuous reagent addition (sensitivity and sampling rate 90 and 83% higher, respectively), the consumption of OPA was 230-fold lower.

Ion pair stabilization effects on a series of procaine structural analogs

In this work, a series of 10 structural procaine analogs have been synthesized in order to investigate the structural features affecting the stability of ion pair formation and its influence on the lipophilicity of ionizable compounds. The structural variation within this series was focused on the terminal nitrogen substituents and on the intermediate chain linkage nature. The hydrophobic parameters log P(n) and log P(i) (partition coefficient of the neutral and ionic species, respectively), as well as the ionization constants pK(a) and pK(a)(oct), were obtained from log D-pH profiles measured at pH values ranging from 2 to 12. The difference between log P(i) and log P(n) values (i.e. difflog P) of each prepared compound was considered a measure of the stability of ion pair formation. In this set, the difflog P values varied nearly over one log unit, ranging from -2.40 to -3.37. It has been observed that the presence of hydrogen bonding groups (especially donor) and low steric hindrance around the terminal amine ionizable group increases the relative lipophilicity of the ionic species as compared to the corresponding neutral species. These results were interpreted as due to the increased stability of ion pairs of the compounds bearing these structural features. (C) 2010 Elsevier B.V. All rights reserved.

Biocompatible in-tube solid phase microextraction coupled with liquid chromatography-fluorescence detection for determination of interferon alpha in plasma samples

The present work demonstrates the successful application of automated biocompatible in-tube solid-phase microextraction coupled with liquid chromatography (in-tube SPME/LC) for determination of interferon alpha(2a) (IFN alpha(2a)) in plasma samples for therapeutic drug monitoring. A restricted access material (RAM, protein-coated silica) was employed for preparation of a lab-made biocompatible in-tube SPME capillary that enables the direct injection of biological fluids as well as the simultaneous exclusion of macromolecules by chemical diffusion barrier and drug pre-concentration. The in-tube SPME variables, such as sample volume, draw/eject volume, number of draw-eject cycles, and desorption mode were optimized, to improve the sensitivity of the proposed method. The IFN alpha(2a) analyses in plasma sample were carried out within 25 min (sample preparation and LC analyses). The response of the proposed method was linear over a dynamic range, from 0.06 to 3.0 MIU mL(-1), with correlation coefficient equal to 0.998. The interday precision of the method presented coefficient of variation lower than 8%. The proposed automated method has adequate analytical sensitivity and selectivity for determination of IFN alpha(2a) in plasma samples for therapeutic drug monitoring. (C) 2010 Elsevier B.V. All rights reserved.

Modeling Information Diffusion in University Libraries: Assessing Peer Interaction Patterns as a Complex Dynamic System

This presentation was offered as part of the CUNY Library Assessment Conference, Reinventing Libraries: Reinventing Assessment, held at the City University of New York in June 2014.

Koldiffusionens inverkan på utmattnings-hållfastheten hos varmvalsade sexkantsstänger;The influence of carbon diffusion on the fatigue strength of hot rolled hexagonal rods

Helstångsborr och konstång kallas bergborrverktyg, som tillverkas av sexkantiga stänger med inre hål för ledning av spolvatten. Dessa spolhål är klädda med ferritiskt rostfritt stål. Innan valsning borras ett centrerat hål i stålämnet som ska valsas. I det borrade hålet appliceras ett rör av ferritiskt rostfritt stål och i det röret skjuts en manganstålskärna in. Efter valsning dras kärnan ut och ett spolhål med invändigt foder av rostfritt stål bildas. Under uppvärmningen och valsningen av stålämnet sker normalt en koldiffusion från manganstålskärnan till det rostfria fodret. Fodrets syfte är att skydda spolhålets yta mot erosion och korrosion.Syftet med arbetet var att hitta en metod som garanterar uppkolning av det invändiga fodret, samt att utreda vad uppkolningen betyder för den mekaniska hållfastheten i stängerna. Ett laboratorieförsök visade att det var bra, med avseende på uppkolning, att blanda stearat i kärnbestrykningsmedlet. Kärnbestrykningsmedlet penslas på manganstålskärnan innan den förs in i stålämnet som ska valsas, dess syfte är att minska friktionen vid kärnutdragningen efter valsning.Ett försök utfördes i valsverket med stearat i kärnbestrykningsmedlet. En grundlig undersökning utfördes på två hetor som valsats med stearat-bestrykningsmedel, samt på en traditionellt tillverkad heta för att ha som referens. Hetorna kapades till provstänger om 1,5 m, totalt undersöktes 55 st.Utvärderingen av verksförsöket visade att stängernas kvalitet blir tillräckligt bra om ingenting oförutsett händer i produktionen, oavsett om koltillskott är tillsatt i bestrykningsmedlet eller inte. Arbetet gav inte en garanterande metod, men visade att stängerna normalt håller hög kvalitet.

Technology diffusion: analysing the diffusion of agent technologies

Despite several examples of deployed agent systems, there remain barriers to the large-scale adoption of agent technologies. In order to understand these barriers, this paper considers aspects of marketing theory which deal with diffusion of innovations and their relevance to the agents domain and the current state of diffusion of agent technologies. In particular, the paper examines the role of standards in the adoption of new technologies, describes the agent standards landscape, and compares the development and diffusion of agent technologies with that of object-oriented programming. The paper also reports on a simulation model developed in order to consider different trajectories for the adoption of agent technologies, with trajectories based on various assumptions regarding industry structure and the existence of competing technology standards. We present details of the simulation model and its assumptions, along with the results of the simulation exercises.

On the statistical estimation of diffusion processes: a survey

Data available on continuos-time diffusions are always sampled discretely in time. In most cases, the likelihood function of the observations is not directly computable. This survey covers a sample of the statistical methods that have been developed to solve this problem. We concentrate on some recent contributions to the literature based on three di§erent approaches to the problem: an improvement of the Euler-Maruyama discretization scheme, the use of Martingale Estimating Functions and the application of Generalized Method of Moments (GMM).

On the statistical estimation of diffusion processes - a partial survey

Data available on continuous-time diffusions are always sampled discretely in time. In most cases, the likelihood function of the observations is not directly computable. This survey covers a sample of the statistical methods that have been developed to solve this problem. We concentrate on some recent contributions to the literature based on three di§erent approaches to the problem: an improvement of the Euler-Maruyama discretization scheme, the employment of Martingale Estimating Functions, and the application of Generalized Method of Moments (GMM).

A (semi-)parametric functional coefficient autoregressive conditional duration model

In this paper, we propose a class of ACD-type models that accommodates overdispersion, intermittent dynamics, multiple regimes, and sign and size asymmetries in financial durations. In particular, our functional coefficient autoregressive conditional duration (FC-ACD) model relies on a smooth-transition autoregressive specification. The motivation lies on the fact that the latter yields a universal approximation if one lets the number of regimes grows without bound. After establishing that the sufficient conditions for strict stationarity do not exclude explosive regimes, we address model identifiability as well as the existence, consistency, and asymptotic normality of the quasi-maximum likelihood (QML) estimator for the FC-ACD model with a fixed number of regimes. In addition, we also discuss how to consistently estimate using a sieve approach a semiparametric variant of the FC-ACD model that takes the number of regimes to infinity. An empirical illustration indicates that our functional coefficient model is flexible enough to model IBM price durations.

Modelagem matemática para o transporte de partículas sujeitas a múltiplos mecanismos de retenção

Discrepancies between classical model predictions and experimental data for deep bed filtration have been reported by various authors. In order to understand these discrepancies, an analytic continuum model for deep bed filtration is proposed. In this model, a filter coefficient is attributed to each distinct retention mechanism (straining, diffusion, gravity interception, etc.). It was shown that these coefficients generally cannot be merged into an effective filter coefficient, as considered in the classical model. Furthermore, the derived analytic solutions for the proposed model were applied for fitting experimental data, and a very good agreement between experimental data and proposed model predictions were obtained. Comparison of the obtained results with empirical correlations allowed identifying the dominant retention mechanisms. In addition, it was shown that the larger the ratio of particle to pore sizes, the more intensive the straining mechanism and the larger the discrepancies between experimental data and classical model predictions. The classical model and proposed model were compared via statistical analysis. The obtained p values allow concluding that the proposed model should be preferred especially when straining plays an important role. In addition, deep bed filtration with finite retention capacity was studied. This work also involves the study of filtration of particles through porous media with a finite capacity of filtration. It was observed, in this case, that is necessary to consider changes in the boundary conditions through time evolution. It was obtained a solution for such a model using different functions of filtration coefficients. Besides that, it was shown how to build a solution for any filtration coefficient. It was seen that, even considering the same filtration coefficient, the classic model and the one here propposed, show different predictions for the concentration of particles retained in the porous media and for the suspended particles at the exit of the media