Sequential injection analysis (SIA) that was developed in 1990 is a simple, versatile and automated technique based on precise aspiration of small volumes of reagents and samples into a single channel. It is economical in terms of reagent consumption and waste generation. SIA is applied to food, environmental and pharmaceutical samples. SIA parameters and the chemical variables are optimized and figures of merit are reported. Spectrophotometer has been used as a detector in the analysis of formaldehyde (HCHO), ascorbic acid and ferric iron (Fe (III)). A stopped flow method was adapted to SIA spectrophometric technique. Enhanced sensitivity was obtained using a stopped flow method as compared to a non-stopped flow method. The SIA spectrophotometric determination of Fe (III) through complex formation with the thiocyanate and the Tiron reagents has been studied in chapter 3. The two methods were compared based on convenience, sensitivity, simplicity, reliability and on general application. Both methods are simple, employ readily available reagents and have lower detection limits and shorter analysis time of 72 samples per hour. The thiocyanate method enabled the determination of Fe (III) in the linear range of 2 to 50 mg/ℓ with a detection limit of 0,2 mg/ℓ whereas the Tiron method provided a linear range of 1 to 50 mg/ℓ with a detection limit of 0,1 mg/ℓ. Chapter 4 presents the application of SIA spectrophotometric method for the determination of formaldehyde in wastewater. The method is based on the inhibition of brilliant green-sulfite reaction by formaldehyde. The kinetic method was implemented by stopping the flow when the complex reaches the detector and the measurements were taken as the reaction proceeds. The SIA method was compared with the chromotropic acid method and the paired t-test was used to determine whether the results obtained by the two methods differ significantly. Good sensitivity with a detection limit of 0,06 mg/ℓ and a wider linear range of 1-3 mg/ℓ was achieved. Chapter 5 describes the indirect determination of ascorbic acid in pharmaceutical samples, sweets and beverage (orange juice). This method is based on reduction of Fe (III) to ferrous iron (Fe (II)) by ascorbic acid under UV-light irradiation and the reaction of generated Fe (II) with 1,10-phenanthroline. The flow was stopped in the holding coil for a defined time to ensure that complete reduction process take place under irradiation. Photochemical reaction methods improved the sensitivity with detection limit of 0,06 mg/ℓ. Good precision was obtained with relative standard deviation of 1,3 %. The method compared well with the N-bromosuccinimide titration method. The versatility and simplicity of SIA technique makes it suitable to different requirements of various analytical problems. / Dissertation (MSc (Chemistry))--University of Pretoria, 2007. / Chemistry / MSc / unrestricted

The concept of sequential injection analysis (SIA), introduced as a simple and convenient principle, has established itself as a well defined analytical technique suitable for routine laboratory analysis. This technique is fully computerized and reliable with a reasonable sample frequency, low sample and reagent consumption and low frequency of maintenance. In pharmaceutical based analysis SIA can be used at each step through the entire production process, from raw material to the final consumer product. With its substantial advantages, an SIA system can replace sophisticated instrumentation facilities, which are unlikely to be used for manufacturing environments. The aim of this study was to investigate the application of the sequential injection analysis technique in the determination of selected substances of biological importance from the pharmaceutical industry (zinc, paracetamol and boron). It is important to control the level of zinc and boron in human, animals and plants. Overdose of paracetamol is a problem in our body. That is why the uniformity tests of paracetamol must be very accurate and precise. The aim was successfully achieved. The results obtained for all substances proved the high reliability of the SIA technique. / Dissertation (MSc (Chemistry))--University of Pretoria, 2006. / Chemistry / unrestricted

Please read the abstract in the section 00front of this document / Thesis (PhD (Chemistry))--University of Pretoria, 2005. / Chemistry / unrestricted

Thesis (Ph. D.)--University of Washington, 2002. / Vita. Includes bibliographical references (leaves 192-197).

El objetivo de esta tesis ha sido estudiar y desarrollar metodologias analíticasusando un sistema de inyección secuencial (SIA) con un espectrofotómetro de diodos enfila para obtener datos de segundo orden. Para tratar estos datos, las herramientasquimiométricas usadas han sido; resolución de curvas multivariante mediante mínimoscuadrados alternados (MCR-ALS) y otras técnicas relacionadas a ésta como el análisisde componentes principales (PCA) y SIMPLISMA. Además se han aplicado estrategiasde diseño de experimentos para obtener las condiciones experimentales óptimas. Estametodología se aplicó a la determinación de amoxicilina y ácido clavulánico enmedicamentos.El primer capítulo de la tesis contiene una descripción de la amoxicilina y del ácidoclavulánico, una explicación de los fundamentos teóricos tanto del sistema instrumentalcomo de las herramientas quimiométricas usadas y por último, se describen los diseñosde experimentos usados y la función de deseabilidad.En los dos siguientes capítulos, se muestran en forma de artículos científicos lostrabajos experimentales realizados. En un primer artículo, se realizó una clasificación delos medicamentos dependiendo si se tenían interferentes o no, para posteriormenteproponer el tipo de calibrado. Un paso previo a la diferenciación de los medicamentos,fue buscar una secuencia analítica que permitiera obtener un sistema en evolución. Estaetapa se llevó a cabo mediante un diseño de experimentos.En el segundo artículo, se determinó la cantidad de amoxicilina en losmedicamentos que tenían interferentes y además no tenían zonas selectivas. Para llevara cabo de forma correcta la etapa de calibración se realizó un estudio de una serie deparámetros asociados a MCR-ALS. En un tercer artículo se realizó la determinaciónsimultánea del ácido clavulánico y de la amoxicilina que poseían unas característicasácido-base y una sensibilidad espectral similar. Por tal de determinar simultáneamenteambos analitos se rediseñó todo el experimental. En el cuarto artículo se hizo unarevisión bibliográfica de ambas técnicas a partir del año 2004 y se discutió el potencial deusar un sistema de inyección secuencial para generar datos de segundo orden.Con la experimentación realizada se comprobó que el paso clave en estasmetodologias era obtener una buen sistema en evolución, es decir diseñar una buenasecuencia analítica. Por lo que se profundizó en estrategias basadas en diseños deexperimentos. En el quinto artículo, se estudiaron qué factores podían afectar a lasecuencia analítica. También se propusieron respuestas que representaran de una formacuantitativa una buena resolución. Se realizó un diseño Plackett-Burman con el objetivode eliminar los factores no relevantes, para posteriormente modelar una superficie derespuesta a partir de los factores relevantes que permite visualizar las condicionesóptimas de la secuencia analítica.El inconveniente de utilizar la metodología de superficie de respuesta es que enlos casos donde el número de factores relevantes sea superior a 3 o 4, el número deexperiencias aumenta considerablemente. En estos casos, una técnica alternativa essimplex que dio lugar a un sexto artículo.El último capítulo de la tesis contiene las conclusiones. Como una conclusióngeneral, se puede decir que la combinación de un sistema de inyección secuencial (SIA)y una herramienta quimiométrica como la resolución de curvas multivariante mediantemínimos cuadrados alternados (MCR-ALS) puede ser usado tanto para realizar unanálisis cualitativo y cuantitativo ya que proporciona información de los perfiles deconcentración y perfiles espectrales de las diferentes especies a estudio. / The objective of this thesis is to study and develop analytical methods to determineamoxicillin and clavulanic acid in pharmaceuticals using sequential injection analysis (SIA)with a diode-array spectrophotometric detector to obtain second-order data. To treat thesedata, the chemometric tool used was; multivariate curve resolution with alternating leastsquares (MCR-ALS) and the techniques involved in the resolution process are: principalanalysis components (PCA) and simple-to-use interactive self-modelling mixture analysis(SIMPLISMA).The first chapter contains a brief description of the theoretical backgrounds thathave been used during this thesis. We explain the characteristics and properties ofamoxicillin and clavulanic acid, we describes the instrumental and the chemometric toolsused and at the end, we introduce the experimental designs used and the desirabilityfunction.In the next two chapters contain the bulk of the work carried out for this thesis andincorporate papers published in journals. In the first paper, the pharmaceuticals wereclassified according to their selective zones in order to propose the type of calibration. In aprevious step, the experimental work was conducted to find an analytical sequence thatallows us to obtain an evolving system. This step was carried out using experimentaldesign. In the second paper, the quantity of amoxicillin in the pharmaceuticals withinterferents or without selective zones was determined. To carry out correctly thecalibration step, we studied different conditions related to the MCR-ALS process.In the third paper, we propose the simultaneous determination of amoxicillin andclavulanic acid which they have the acid-base characteristics and spectral profile similar.To determine both analytes, a new analytical sequence was redesigned. In the fourthpaper, we describe the state of the art of sequential injection analysis (SIA) andmultivariate curve resolution with alternating least squares (MCR-ALS) by reviewing thebibliography since 2004. We discuss the potential of SIA for generating second-orderdata.In previous papers, we found that the most critical step in the development ofanalytical methods based on SIA and MCR-ALS was to obtain an analytical sequence thatprovides an evolving system. To resolve so, we developed the method of experimentaldesign to obtain the optimal analytical sequence.In the forth paper, we studied all the factors and analysed how they affect to theanalytical sequence. We also proposed responses to quantitatively represent a goodresolution. Once these factors and responses were proposed, we used a Plackett-Burmandesign to remove the non-relevant factors and then modelled a response surface. In themaximum of response surface, the optimum conditions for the analytical sequence couldbe visualised. To transform several responses into a single response, we used the overalldesirability function. In the sixth paper, we applied an alternative optimisation methodknows as the simplex approach. We aimed to determine amoxicillin and clavulanic acidsimultaneously when the number of factors and responses was higher than in theprevious paper.The last chapter contains the conclusions of the thesis. In general, we concludethat a combined sequential injection analysis (SIA) with a multivariate detector (i.e. diodearray spectrophotometer) and multivariate curve resolution with alternating least squares(MCR-ALS) can be used for both qualitative and quantitative analyses since, it providesconcentration and spectra profiles for the different species of the sample.

Please read the abstract in the section 00front of this document / Dissertation (MSc (Chemistry))--University of Pretoria, 2005. / Chemistry / unrestricted

Here we report vertical profiles of dissolved (0.2 um filtered) Aluminum (Al) for eight stations in the Beaufort Sea in the Canadian Arctic, six of which are along a transect extending from the coastal shelf northeast of the Mackenzie River delta out to the Beaufort Sea. Sampling was performed aboard the CCGS Sir Wilfrid Laurier in September 2007 and all analyses were performed in a Class 100 clean space at the University of Victoria. Vertical profiles of dissolved Al in the water column displayed surface maxima, subsurface minima and a general increase in concentration with depth as is characteristic of a “scavenged” trace element in seawater. Concentrations of dissolved Al for the upper 1000 m were generally low ranging from the < 1 nmol kg-1 observed in the sub-surface minimum corresponding to the Pacific inflow layer and increasing to ~6-10 nmol kg-1 with depth. The surface maxima at stations for Al was associated with relatively fresh surface water (26-30 PSS) that is believed to be the result of seasonal sea-ice melt. This correlation suggests that the melting of sea-ice with entrained sediments may be an important mechanism for the delivery of Al and associated trace metals to the water column of the Beaufort Sea. We also report measurements of “total Al” (unfiltered and acidified to pH 1.7 for two year prior to analysis) for the Arctic Ocean which indicate that a significant proportion of Al in the water column is present in the > 0.2 um fraction. These measurements and the hydrographic data along the transect indicate the transport of a cold, saline, metal enriched water mass off of the continental shelf into the Canada Basin. This water mass appears to reflect the return of cold, high salinity slope water originally emplaced on the shelf by upwelling favourable winds. Alternatively, this water mass may be the product of brine exclusion from sea-ice formation during the previous winter that was unable to vacate the shelf due to the persistent upwelling observed throughout 2007. This finding suggests that the convection of cold, dense shelf water may be a mechanism for supplying the deep waters of the Arctic with an injection of water containing a significant Al content. In addition, a low volume sequential injection analysis (SIA) method is proposed for determination of elevated concentrations of Al, like those typically observed in coastal and river waters. A thorough optimization of the chemistry and instrumental parameters was performed along with an extensive investigation into potential interferents. The method was found to be largely free of interferents at environmentally relevant concentrations and was determined to have a detection limit of 24 nM. The precision of the method was reported to be 2% at 75 nmol kg-1 and analysis of the SLRS-4 certified reference material validated the accuracy of the method. Analysis of several samples that were previously analyzed via flow injection analysis (FIA) and standardized with consensus values of an open ocean reference material indicated the method returned comparable values for the Al concentration in the samples. Development and optimization of the SIA has resulted in an accurate and precise low-cost method of analysis that is both sensitive and relatively free from interference for the detection of nano-molar levels of Al in coastal and natural waters.

Please read the abstract in the section 00front of this document / Thesis (PhD)--University of Pretoria, 2010. / Chemistry / unrestricted

This thesis deals with the optimization determination of chondroitin sulfate sequential injection analysis with spectrophotometric detection. The reaction proceeds in the presence of phenothiazine cationic dyes (Azure A, Azure B and methylene blue) and measuring the decrease absorbance dyes in their absorption maximum after the addition of chondroitin sulfate. Have found the optimum conditions for this determination: dye concentration 5 10-5 mole dm-3 , the dosing volume 100 µl CS + 50 µl dye + 100 µl CS, reaction time 0 s, flow rate 40 µl s-1 . For the determination of the CS in a static arrangement was found the lowest limit of detection and quantification using metylene blue (LOD = 0,23 mg l-1 a LOQ = 0,76 mg l- 1 ). The best repeatibility was achieved also using methylene blue 2,4 %. On the other side the best sensitivity was achieved using azure A. For the determination of the CS in SIA arrangement was found the lowest limit of detection and quantification using azure (LOD = 0,34 mg l-1 a LOQ =1,01 mg l-1 ). The best repeatibility was achieved also using azure A 1,9 %. And the best sensitivity was achieved using azure B. Based on these findings was chondroitin sulphate determined in food supplements, the more suitable method were the calibration curve .The determination was also carried out...

Esta dissertação descreve o uso de técnicas eletroanalíticas em fluxo no estudo da adsorção de Cd(II), Pb(II) e Cu(II) em vermiculita visando tratamento alternativo para efluentes da indústria de tintas. O estudo indicou que na faixa de pH entre 4 e 6 não há diferença entre a utilização de vermiculita expandida ou não-expandida na remoção dos íons. Observou-se que nos pH\'s avaliados o tempo de interação de 180 minutos foi suficiente para que o sistema atingisse o equilíbrio. Pode-se afirmar que a vermiculita não expandida apresenta as seguintes ordens de afinidade pelo cátions considerados: pH 4: Cu(II) < Cd(II) < Pb(II); pH 5: Cu(II) ? Cd(II) < Pb(II); pH 6: Cd(II) < Cu(II) < Pb(II). Nas condições de trabalho, os ensaios envolvendo a coluna de vermiculita não evidenciaram uma melhor capacidade de extração dos íons estudados frente ao sistema de extração em batelada. Percentuais de extração da ordem de 76% em amostra de efluente no sistema em batelada reforçam a viabilidade do uso da vermiculita como adsorvente destes metais. Um método SIA-ASV (análise por injeção seqüencial - voltametria de redissolução anódica) foi proposto e validado. Para um tempo de deposição de 80 s e vazão de 10 µLs-1, os limites de detecção foram 0,06, 0,09 e 0,16 µmolL-1 para Cd, Pb e Cu, respectivamente, além de apresentar uma faixa linear de trabalho entre 0,2 e 9,0 µmolL-1. / This dissertation describes the use of flow electroanalytical techniques to study the adsorption of Cd(II), Pb(II) and Cu(II) onto vermiculite aiming an alternative treatment of wastewater from coatings industry. The study indicated that under pH range from 4 to 6 there is no difference on using expanded or not expanded vermiculite for removal of ions. It was also observed that at any evaluated pH, a 180 minutes interaction time was long enough to allow the system reach equilibrium. It\'s possible to state that non-expanded vermiculite presents the following affinity orders by the studied ions: pH 4: Cu(II) < Cd(II) < Pb(II); pH 5: Cu(II) ? Cd(II) < Pb(II); pH 6: Cd(II) < Cu(II) < Pb(II). At working conditions, tests involving vermiculite columns didn\'t show a better performance on extracting these ions when faced to batch extraction systems. Extraction percentuals of about 76% were obtained using a sample of coatings industry wastewater, reinforcing the viability of the use of vermiculite as an adsorbent of these metals. A SIA-ASV (sequential injection analysis - anodic stripping voltammetry) method was proposed and validated. For a deposition time of 80 s and a flow rate of 10 µL s-1, detection limits were 0.06, 0.09 and 0.16 µmol L-1 to Cd, Pb and Cu, respectively; a linear working range, between 0.2 and 9.0 µmol L-1 was also determined.