<p>U okviru ove doktorske disertacije razvijene su elektroanalitičke metode za određivanje pojedinih vitamina B grupe. Za određivanje vitamina B₁ i B₃ primenjena je adsorpciona hronopotenciometrijska striping analiza (AdHSA) na tankoslojnoj živinoj elektrodi kao radnoj elektrodi, dok je za određivanje vitamina B2 primenjena hronopotenciometrijska analiza (HA) na dvema geometrijski različitim elektrodama od staklastog ugljenika: planarnoj disk elektrodi i elektrodi u vidu procesne posude. U cilju optimizacije metoda ispitan je uticaj najznačajnijih eksperimentalnih faktora. Optimalni eksperimentalni uslovi za određivanje vitamina B₁ su podrazumevali primenu 0,2 mol/l citratnog pufera vrednosti pH 6 kao pomoćnog elektrolita, potencijala i vremena akumulacije od -1,313 V i 50 s, redom, i struje rastvaranja depozita od 1,9 &ndash; 6,1 &mu;A. Odgovarajući eksperimentalni faktori za određivanje vitamina B₂ su bili: 0,025 mol/l HCl kao pomoćni elektrolit, inicijalni potencijal od 0,023 V i struja redukcije od 0,8 &ndash; 4,2 &mu;A, dok su optimalni radni uslovi za određivanje vitamina B₃ obuhvatali primenu 0,05 mol/l citratnog pufera pH 6, potencijala akumulacije od -1,405 V pri vremenu akumulacije od 15 s, i struji rastvaranja u intervalu od 1,4 &ndash; 15,1 &mu;A. U slučaju određivanja vitamina B₂ primenom radne elektrode u vidu procesne posude ispitan je i uticaj aktivne povr&scaron;ine radne elektrode na analitički signal vitamina B₂. Optimalna vrednost aktivne povr&scaron;ine radne elektrode iznosila je 13,4 cm². Pod optimalnim eksperimentalnim uslovima, dolazilo je do elektrooksidacije molekula vitamina B₁ i B₃ na tankoslojnoj živinoj elektrodi u analitičkom koraku, dok se vitamin B₂ redukovao na elektrodama od staklastog ugljenika. U okviru validacije metoda definisani su opsezi linearnosti, određene su vrednosti granice detekcije i granice kvantitativnog određivanja, ocenjena je preciznost i ispitane su interferencije. Uz odgovarajuće uslove rada, dobijena je dobra linearnost analitičkog signala od sadržaja za sva tri ispitivana vitamina. Ostvarene su granice detekcije od 1,64 mg/l za vitamin B₁, 0,076 mg/l za vitamin B₂ uz primenu planarne disk elektrode i 0,018 mg/l (vitamin B₂) uz primenu procesne posude od staklastog ugljenika kao radne elektrode. Ostvarena granica detekcije za vitamin B₃ je iznosila 2,20 mg/l. Nakon optimizacije i validacije, razvijene metode HA i AdHSA primenjene su za određivanje vitamina B₁, B₂ i B₃ u komercijalnim multivitaminskim dodacima ishrani i multivitaminskim instant napicima. Tačnost razvijenih metoda je potvrđena paralelnim analizama izvedenim primenom visokopritisne tečne hromatografije.</p> / <p>Within the scope of this doctoral dissertation, electroanalytical methods for the determination of several vitamins of the B-complex are developed. For the determination of vitamin B1 and B3 adsorptive chronopotentiometric stripping analysis was applied, with mercury film electrode as the working electrode. For vitamin B2 determination, the chronopotentiometric analysis was performed on two geometrically different glassy carbon working electrodes: the planar disc electrode and the process vessel electrode. The most important experimental parameters of the analysis were investigated and optimized. For vitamin B₁ determination, the optimized experimental conditions were: 0,2 mol/l citrate buffer pH 6 as the supporting electrolyte, accumulation potential of -1,313 V, accumulation time of 15 s and the oxidation current between 1,9 &mu;A and 6,1 &mu;A. The appropriate experimental factors for vitamin B₂ determination included 0,025 mol/l HCl solution (supporting electrolyte), initial potential of 0,023 V and reduction current in the range from 0,8 &ndash; 4,2 &mu;A, whereas the optimal working parameters for vitamin B3 determination were as follows:0,05 mol/l citrate buffer pH 6, accumulation potential of -1,405 V, accumulation time of 15 s and dissolution current from 1.4 &ndash; 15.1 &mu;A. When the process vessel was used as the working electrode, the optimal volume of the analyzed solution i.e. the active surface area of the electrode was optimized. The optimal value of the active surface area was 13,4 cm2. As well, under the optimal experimental conditions, vitamin B₁ and vitamin B3 underwent electrooxidation process in the analytical step, whereas vitamin B₂ was electrochemically reduced on glassy carbon electrodes. A validation procedure of the optimized methods was performed by evaluation of the following parameters: linearity, the limit of detection (LOD), the limit of quantitation (LOQ), precision, selectivity, and accuracy. Under optimal working conditions, the linearity of the proposed methods was very good. The achieved limits of detection were 1.64 mg/l for vitamin B₁, 0,076 mg/l for vitamin B₂ (planar disc electrode) and 0,018 mg/l (process vessel electrode) and 2,2 mg/l for vitamin B₃.<br />After optimization and validation procedures, the developed methods were applied for vitamin B₁, B₂, and vitamin B₃ determination in commercially available multivitamin supplements and instant multivitamin beverages. The accuracy of the proposed methods was tested by parallel HPLC analyses of the same samples.</p>

Objective: The goal of this research was to determine whether alternate-line shading (zebra-striping) of grid-based displays affects the strategy (i.e., “visual flow”) and efficiency of serial search. Background: Grids, matrices, and tables are commonly used to organize information. A number of design techniques and psychological principles are relevant to how viewers’ eyes can be guided through such visual works. One common technique for grids, “zebra-striping,” is intended to guide eyes through the design, or “create visual flow” by alternating shaded and unshaded rows or columns. Method: 13 participants completed a visual serial search task. The target was embedded in a grid that had 1) no shading, 2) shading of alternating rows, or 3) shading of alternating columns. Response times and error rates were analyzed to determine search strategy and efficiency. Results: Our analysis found evidence supporting a weak effect of shading on search strategy. The direction of shading had an impact on which parts of the grid were responded to most rapidly. However, a left-to-right reading bias and middle-to-outside edge effect were also found. Overall performance was reliably better when the grid had no shading. Exploratory analyses suggest individual differences may be a factor. Conclusion: Shading seems to create visual flow that is relatively weak compared to search strategies related to the edge effect or left-to-right reading biases. In general, however, the presence of any type of shading reduced search performance. Application: Designers creating a grid-based display should not automatically assume that shading will change viewers search strategies. Furthermore, although strategic shading may be useful for tasks other than that studied here, our current data indicate that shading can actually be detrimental to visual search for complex (i.e., conjunctive) targets.

<p>U radu su definisani najznačajniji ekspirementalni faktori hronopotenciometrijske striping analize žive na staklastom ugljeniku. Poređeni su različiti elektrohemijski sistemi. Ispitani sistemi su obuhvatili klasičnu elektrohemijsku ćeliju sa stacionarnom disk elektrodom, sistem sa rotirajućom disk elektrodom, procesnu posudu od staklastog ugljenika kao radnuelektrodu i protočne sisteme uz tankoslojnu i tubularnu ćeliju.</p><p>Tačnost definisanih metoda je potvrđena analizom standardnog referentnog materijala - lista paradajza. Najveća osetljivost određivanja žive je postignuta primenom procesne ča&scaron;e od staklastog ugljenika kao radne elektrode. Granica detekcije je iznosila 0,10ng/dm^3&nbsp;žive(II). Razvijene metode su primenjene za određivanje žive u vodama. Uzorci voda su obuhvatili vode za piće, morske, rečne, bunarske, jezerske i otpadne vode.</p> / <p>In this work optimal experimental conditions of chronopotentiometric stripping analysis of mercury using glassy carbon were investigated. Critical review of different electrochemical systems is given. Conventional electrochemical cell with stationary disc electrode, cell with rotating disc elektrode, system with process vessel as a working electrode and flow systems with thin-layer and tubular cell were encompassed by the investigation.</p><p>Accuracy of the particular techniques was confirmed by analysing standard reference material - tomato leaves. Best sensitivity was achieved using process vessel of glassy carbon as a working electrode - 0,1 ng/d³. The developed methods were used for water analysis. Mercury was determined in samples of tap, well, seawater, river, lake, rain waters and in one sample of waste water.</p>

Manual inspection is a prevailing practice for quality assessment of poultry meat, but it is labor-intensive, tedious, and subjective. This thesis aims to assess the efficacy of an emerging structured illumination reflectance imaging (SIRI) technique with machine learning approaches for assessing WS and microbial spoilage in broiler breast meat. Broiler breast meat samples were imaged by an in house-assembled SIRI platform under sinusoidal illumination. In first experiment, handcrafted texture features were extracted from direct component (DC, corresponding to conventional uniform illumination) and amplitude component (AC, unique to the use of sinusoidal illumination) images retrieved from raw SIRI pattern images build linear discriminant analysis (LDA) models for classifying normal and defective samples. A further validation experiment was performed using deep learning as a feature extractor followed by LDA. The third experiment was on microbial spoilage assessment of broiler meat, deep learning models were used to extract features from DC and AC images builds on classifiers. Overall, this research has demonstrated consistent improvements of AC over DC images in assessing WS and spoilage of broiler meat and that SIRI is a promising tool for poultry meat quality detection.

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Tesis por compendio / Food industry has evolved remarkably during the last decades due to the need to technify the production with the aim of reducing processing times and to increase industry profits, without this implying a decrease of the product quality. In this context, the use of spectrophotometric monitoring and treatment techniques for the optimization of production processes can represent a great progress for agri-food industry. In block 1, animal tissues were studied. Firstly, the use of spectrophotometric sensors for the control of pork meat drying. In this context, two techniques were used, infrared thermography and microwave monitoring. This study, coupled to a thermodynamic model and some physicochemical determinations have shown that infrared thermography is a suitable technique able to monitor drying process, identifying each drying stage. On the other hand, in microwave range, (500 MHz to 20 GHz) and it was demonstrated that the loss factor in gamma-dispersion has a direct relation with the number of molecules on the meat sample surface. A non-destructive and easy-to-use sensor in radiofrequency range able to detect if meat samples has been suffered freeze/thaw cycles has been developed. An exhaustive study was carried out to solve the problems resulting from the strong technification and intensification in poultry industry, such as low-quality meats (PSE and DFD), the white striping and the deep pectoral myopathies, mainly produced because of the use of hypertrophic strains. For each of these problems, spectrophotometric studies were performed in the radiofrequency and microwave ranges and they were related to physicochemical and biochemical parameters, obtaining the relaxation parameters for alfa, beta and gamma-dispersions by using a logistic model. Sensors were developed in radiofrequency range, and in addition, for the myopathy studies, the developed sensors were able even to measure through the skin in whole chicken carcasses. In Block 2 plant tissues were studied. Firstly, the tissues that compose the mandarin were characterized spectrophotometrically. Due to this, a physicochemical and structural study were coupled with the permittivity obtained in radiofrequency and microwave ranges. As one of the most important results of this research, a tool based on the dielectric relaxation constant in the gamma-dispersion able to predict the moisture of the samples was obtained. Secondly, the study of the application of pulsed electric fields as a pre-treatment to the osmotic dehydration of kiwifruit was carried out. This technique, coupled with physicochemical determinations and a thermodynamic study, has demonstrated that the pulsed electric fields accelerate the osmotic dehydration process, mainly due to the cells plasmolyzation. In addition, the monitoring of the process was carried out with NMR, where the internal transports and the transformations that the plant tissue suffers were analysed. Finally, it has been possible to conclude that NMR is a suitable technique to quantify the water molecules according to their location in the tissue and to obtain sorption isotherms throughout the complete range of water activities. Finally, block 3 focuses on colloidal systems. Particularly, the stability of high-value bioactive compounds (beta-galactosidase) by its encapsulation in alginate-Ca(II) hydrogels with and without the addition of secondary excipients was studied. In this study, the microstrucure by SAXS and SEM was analyzed, also enzimatic activity against thermal treatments and by NMR. / La industria agroalimentaria ha evolucionado notablemente durante las últimas décadas debido a la necesidad de tecnificar la producción con el objetivo de reducir los tiempos del proceso y aumentar las ganancias de las industrias, sin que ello suponga una disminución de la calidad del producto. En este contexto, la utilización de técnicas espectrofotométricas de monitorización y tratamiento para la optimización de procesos productivos pueden suponer un gran avance para la industria agroalimentaria. En el bloque 1, se realizaron estudios en tejidos animales. En primer lugar, se analizó la utilización de sensores espectrofotométricos para el control del secado de la carne de cerdo. Para ello, se utilizaron dos técnicas, la termografía infrarroja y la monitorización por microondas. Este estudio, acoplado a un modelo termodinámico y determinaciones fisicoquímicas han demostrado que la termografía infrarroja es una técnica capaz de monitorizar el proceso de secado, identificando cada etapa del mismo. En el rango de las microondas (500 MHz a 20 GHz) ha sido posible demostrar que el factor de pérdidas en la dispersión-gamma presenta una relación directa con el número de moléculas de agua en la superficie de la muestra de carne. Se ha desarrollado un sensor no destructivo y de fácil utilización en el rango de la radiofrecuencia, capaz de detectar si las muestras de carne de cerdo han sufrido ciclos de congelación/descongelación. Se realizó un exhaustivo estudio que solventa las problemáticas resultantes de una fuerte tecnificación e intensificación en la industria avícola, como son las carnes de baja calidad (PSE y DFD), la miopatía de las estrías blancas y del pectoral profundo, producidas principalmente como consecuencia de la utilización de estirpes hipertróficas. Para cada una de estas problemáticas, se realizaron estudios espectrofotométricos en los rangos de la radiofrecuencia y de las microondas y se relacionaron con parámetros fisicoquímicos y bioquímicos, obteniendo los parámetros de relajación para las dispersiones alfa, beta y gamma mediante un modelo logístico. Se desarrollaron sensores en el rango de la radiofrecuencia capaces de detectarlas, y además, para el estudio de las miopatías, los sensores desarrollados son capaces de medir inclusive a través de la piel en carcasas de pollo enteras. En el bloque 2 se abordan estudios en tejidos vegetales. En primer lugar, se caracterizaron espectrofotométricamente los tejidos que componen la mandarina. Es por ello, que de forma conjunta a un estudio fisicoquímico y estructural se obtuvieron los valores de la permitividad en radiofrecuencia y microondas. Como uno de los resultados más importantes de esta investigación se obtuvo una herramienta basada en la constante dieléctrica de relajación en la dispersión-gamma capaz de predecir la humedad de las muestras. En segundo lugar, se abordó el estudio de la aplicación de campos eléctricos pulsados como pre-tratamiento a la deshidratación osmótica del kiwi. Esta técnica, acoplada a determinaciones fisicoquímicas y un estudio termodinámico han permitido acelerar el proceso de deshidratación osmótica debido principalmente a la plasmolización de las células. La monitorización del proceso mediante NMR, para analizar los transportes internos y las transformaciones que sufre el tejido en su interior. Por último, se ha podido concluir que la NMR es una técnica adecuada para cuantificar las moléculas de agua de acuerdo a su situación dentro del tejido además de poder ser utilizada para obtener isotermas de sorción en todo el rango de actividades de agua. El bloque 3 se centra en los sistemas coloidales. Se busca aumentar la estabilidad de compuestos bioactivos de alto valor (beta-galactosidasa) mediante su encapsulación en hidrogeles de alginato-Ca(II) con y sin el agregado de excipientes secundarios. En este estudio se evaluó la microestructura mediante SAXS y SEM y / La indústria agroalimentària ha evolucionat notablement durant les últimes dècades a causa de la necessitat de tecnificar la producció amb l'objectiu de reduir els temps del procés i augmentar els guanys de les indústries, sense que això suposi una disminució de la qualitat del producte. En aquest context, la utilització de tècniques espectrofotomètriques de monitorització i tractament per a l'optimització de processos productius poden suposar un gran avanç per a la indústria agroalimentària. Al bloc 1, es van realitzar estudis en teixits animals. En primer lloc, es va analitzar la utilització de sensors espectrofotomètrics per al control de l'assecat de la carn de porc. Per a això, es van utilitzar dues tècniques, la termografia infraroja i el monitoratge per microones. Aquest estudi, acoblat a un model termodinàmic i determinacions fisicoquímiques han demostrat que la termografia infraroja és una tècnica capaç de monitoritzar el procés d'assecat, identificant cada etapa del mateix. En el rang de les microones (500 MHz a 20 GHz) ha estat possible demostrar que el factor de pèrdues en la dispersió-gamma presenta una relació directa amb el nombre de molècules d'aigua a la superfície de la mostra de carn. S'ha desenvolupat un sensor no destructiu i de fàcil utilització en el rang de la radiofreqüència, capaç de detectar si les mostres de carn de porc han patit cicles de congelació / descongelació. Es va realitzar un exhaustiu estudi que soluciona les problemàtiques resultants d'una forta tecnificació i intensificació en la indústria avícola, com són les carns de baixa qualitat (PSE i DFD), la miopatia de les estries blanques i del pectoral profund, produïdes principalment com a conseqüència de la utilització d'estirps hipertròfiques. Per a cadascuna d'aquestes problemàtiques, es van realitzar estudis espectrofotomètrics en els rangs de la radiofreqüència i de les microones i es van relacionar amb paràmetres fisicoquímics i bioquímics, obtenint els paràmetres de relaxació per a les dispersions alfa, beta i gamma mitjançant un model logístic. Es van desenvolupar sensors en el rang de la radiofreqüència capaços de detectar-les, ia més, per a l'estudi de les miopaties, els sensors desenvolupats són capaços de mesurar inclusivament a través de la pell en carcasses de pollastre senceres. Al bloc 2 s'aborden estudis en teixits vegetals. En primer lloc, es van caracteritzar espectrofotomètricament els teixits que componen la mandarina. És per això, que de manera conjunta a un estudi fisicoquímic i estructural es van obtenir els valors de la permitivitat en radiofreqüència i microones. Com un dels resultats més importants d'aquesta investigació es va obtenir una eina basada en la constant dielèctrica de relaxació a la dispersió-gamma capaç de predir la humitat de les mostres. En segon lloc, es va abordar l'estudi de l'aplicació de camps elèctrics premuts com pretractament a la deshidratació osmòtica del kiwi. Aquesta tècnica, acoblada a determinacions fisicoquímiques i un estudi termodinàmic han permès accelerar el procés de deshidratació osmòtica degut principalment a la plasmolización de les cèl·lules. El monitoratge del procés mitjançant NMR, per analitzar els transports interns i les transformacions que pateix el teixit al seu interior. Finalment, s'ha pogut concloure que la NMR és una tècnica adequada per quantificar les molècules d'aigua d'acord a la seva situació dins el teixit més de poder ser utilitzada per obtenir isotermes de sorció en tot el rang d'activitats d'aigua. El bloc 3 se centra en els sistemes col·loïdals. Es busca augmentar l'estabilitat de compostos bioactius d'alt valor (beta-galactosidasa) mitjançant la seva encapsulació en hidrogels d'alginat-Ca (II) amb i sense l'agregat d'excipients secundaris. En aquest estudi es va avaluar la microestructura mitjançant SAXS i SEM i es va estudiar l'activitat enzimàtic / Traffano Schiffo, MV. (2017). Espectrofotometría de baja frecuencia aplicada a sistemas alimentarios [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/90441 / Compendio

<p>Danas, u raznim analitičkim laboratorijama postoji veći broj analitičkih protokola,<br />zasnovanih bilo na izuzetno sofisticiranim ili jednostavnijim tehnikama, koji služe za<br />određivanje različitih ciljnih analita od farmakolo&scaron;kog značaja. Među tim grupama ciljnih analita pripadaju i antibiotici koji predstavljaju veliko otkriće u oblasti medicine i zahvaljujući njima spa&scaron;eno je vi&scaron;e od sedam miliona života, ali pored navedenih koristi, antibiotici mogu da izazovu&nbsp; veliki broj neželjenih efekata i žučne kiseline zajedno sa svojim derivatima, koji su fiziolo&scaron;ki deterdženti, mogu biti citotoksične za organizam ako se njihova koncentracija ne kontroli&scaron;e. U ovoj doktorskoj disertaciji prikazan je razvoj analitičkih metoda pre svega voltametrijskihmetoda u kombinaciji sa jednostavnim i savremenim elektrodama/senzorima za određivanje&nbsp; odabranih analita kao &scaron;to je antraciklični antibiotik doksorubicin (DOX), makrolidni antibiotici<br />eritromicin-etilsukcinata (EES), azitromicina (AZI), klaritromicina (CLA) i roksitromicina&nbsp; (ROX) i 3-dehidro-deoksiholne kiseline.</p><p>Voltametrijska karakterizacija i određivanje gore navedenih antibiotika primenom obnovljive srebro-amalgam film elektrode (Hg(Ag)FE)rađena je direktnom katodnom&nbsp; voltametrijom sa pravougaonim talasima (SWV) i visoko osetljivom adsorptivnom voltametrijom sa pravougaonim talasima (SW-AdSV) u Briton-Robinson puferu, kao pomoćnom elektrolitu, obuhvatajući &scaron;irok opseg pH vrednosti. Odgovor DOX-a primenom&nbsp; Hg(Ag)FE&nbsp;praćen je u intervalu potencijala od -0,20 do -0,80 V.&nbsp; Za analizu tragova, optimizacija metode ukazuje da su optimalni parametri za analitički pik na potencijalu (Ep ) -0,57 V u odnosu na zasićenu kalomelovu elektrodu (ZKE): pH 6,0, potencijal&nbsp; akumulacije -0,20 V i vreme&nbsp; akumulacije 140 s. U model rastvoru, DOX je određivan u koncentracionom opsegu 4,99-59,64&nbsp; ng mL^-1. Razvijena SW-AdSV metoda je primenjena za određivanje DOX-a u obogaćenom uzorku humanog urina. Niža koncentracija DOX-a 9,89ng mL^-1&nbsp;u voltametrijskoj&nbsp; ćeliji je određivana sa relativnom standardnom devijacijom (RSD) manjom od 6,0%. &Scaron;to se ispitivanih makrolida tiče oni su pokazali redukcione signale u dalekoj negativnoj oblasti potencijala. Ispitivanja direktnom katodnom SWV rađena su u opsegu potencijala od -0,75 V do -2,00 V u odnosu na ZKE, pri čemu su dobijena jedan ili dva redukciona pika u opsegu potencijala od -1,5 V do -1,9 V. Oblik i intenzitet signala zavisi od primenjene pH vrednosti u &scaron;irokoj pH oblasti. Za analitičke svrhe, radi razvoja direktne katodne SWV i adsorptivne inverzne/striping SWV metode, pogodnim su se pokazale neutralna i slabo alkalna sredina tj. pH 7,0 sa&nbsp; E_p na -1,67 V u odnosu na ZKE za ROX i EES i pH 7,2 sa E_p na -1,85 V u odnosu na ZKE za AZI i pH 7,4 sa E_p na -1,64 V u odnosu na ZKE za CLA. Na osnovu snimljenih cikličnih voltamograma na&nbsp; optimalnim pH vrednostima, može se predložiti adsorptivno-kontrolisan kinetički proces na elektrodi u slučaju sva&nbsp; četiri ispitivana jedinjenja. Takođe,&nbsp; ¹H NMR merenja uz potiskivanje&nbsp; signala vode u pH oblasti između pH 6,0 i 10,5 ukazuju na to da su makrolidni molekuli pri optimalnim analitičkim uslovima predominantno u protonovanoj formi preko tercijerne amino grupe &scaron;to potpomaže, u sva&nbsp; četiri slučaja, njihovu adsorpciju na odgovarajuće polarizovanoj Hg(Ag)FE. Optimizovane direktne katodne SWV metode&nbsp; pokazuju dobru linearnost u koncentracionom opsegu 4,81-23,3&nbsp; &micro;g mL^-1 , 4,53-29,8&nbsp; &micro;g mL^-1 , 1,96-28,6&nbsp; &micro;g mL^-1 i 1,48-25,9 &micro;g mL^-1 za AZI, EES, CLA odnosno ROX. Razvijene SW-AdSV metode rezultiraju u linearnom odgovoru pri nižim koncentracionim intervalima 1,0-2,46 &micro;g mL^-1 ,&nbsp; 0,69-2,44&nbsp; &micro;g mL^-1, 0,05-0,99 &micro;g mL^-1 i 0,10-0,99&nbsp; &micro;g mL^-1 , za AZI, EES, CLA i ROX. RSD za sve razvijene metode nije veća od 1,5% izuzev SWV metode u slučaju AZI-a gde je 4,5%. Direktna katodna SWV metoda&nbsp; je uspe&scaron;no primenjena za određivanje EES-a u farmaceutskom proizvodu Eritromicin^&reg; dok SW-AdSV metoda je primenjena u slučaju određivanja EES-a u obogaćenom uzorku humanog urina i&nbsp;za određivanje ROX-a u farmaceutskom proizvodu Runac^&reg; . U svim pomenutim slučajevima, primenjena je metoda standardnog dodatka. Pouzdanost i tačnost elaboriranih procedura u slučaju određivanja EES-a u model sistemu i&nbsp; farmaceutskom proizvodu Eritromicin^&reg; su potvrđena poređenjem sa rezultatima dobijenim primenom HPLC-DAD metode.</p><p>Nakon preliminarnih studija 3-dehidro-deoksiholne&nbsp; kiseline/3-dehidro-deoksiholata primenom elektrode od staklastog ugljenika (GCE), gde je uočeno da ne dolazi do formiranja redukcionog signala u Briton-Robinson puferu između pH 5,0 i 11,8 primenom direktne katodne SWV, bizmut-film je izdvojen&nbsp; <em>ex situ</em> na povr&scaron;ini iste elektrode od staklastog ugljenika (BiF-GCE) iz uobičajeno kori&scaron;ćenog rastvora za elektrodepoziciju (0,02 mol L^-1 Bi(NO₃)₃, 1,0 mol L^-1 HCl i 0,5 mol L^-1 KBr) i tako pripremljena elektroda je primenjena za karakterizaciju i određivanje pomenutog jedinjenja u alkalnoj sredini. Redukcioni signal ispitivanog analita od analitičkog značaja je uočen jedino primenom BiF-GCE u Briton-Robinson puferusa pH vrednostima između 9,5 i 11,8 u režimu adsorptivne inverzne/stripingvoltametrije sa pravougaonim talasima, dok u slučaju direktnih katodnih SWV eksperimentalnih uslova uočen je slab redukcioni pik sa niskom strujom maksimuma pika. Optimizovani eksperimentalni uslovi za određivanje 3-dehidro-deoksiholata obuhvataju odgovarajuće kondicioniranje elektrode uključujući kondicioniranje&nbsp; <em>ex situ</em> pripremljene BiF-GCE u Briton-Robinson pomoćnom elektrolitu pH 11,8 do stabilizacije struje bazne linije elektrohemijskim cikliranjem potencijala radne elektrode u potencijalskom opsegu između -1,00 i -2,00 V u odnosu na ZKE (blizu 15 puta) i primenu dva ključna parametara adsorptivne voltametrije sa pravougaonim talasima: vreme akumulacije od 30 s i potencijal akumulacije&nbsp; -1,00 V u odnosu na ZKE. Zbog relativne asimetričnosti dobijenih redukcionih signala ispitivanog analita sa&nbsp; E_p na -1,35 V u odnosu na ZKE, &scaron;to je takođe prisutno i u slučaju primene SW-AdSV, određivanje ispitivanog analita je zasnovano na linearnoj zavisnosti između povr&scaron;ine pika redukcionog signala&nbsp; spitivanog analita i njegove odgovarajuće koncentracije i postignuta granica detekcije je 1,43 &micro;g mL^-1 sa dva linearna opsega kalibracione krive od 4,76 &micro;g mL^-1 do 13,0 &micro;g mL^-1 i od 13,0 &micro;g mL^-1 do 23,1 &micro;g mL^-1 za razvoj analitičke metode. RSD metode je 3,22%. Dodatni eksperimenti, elektroliza ispitivanog analita na potencijalu -1,55 V (blizu maksimuma pika ciljnog analita) u odnosu na ZKE su rađeni primenom GCE u obliku ploče (povr&scaron;ina 33,52 cm 2 ) modifikovane sa&nbsp; <em>ex situ&nbsp;</em>pripremljenim bizmut-filmom. Rastvor od interesa uzorkovan je na početku eksperimenta, nakon 2,5 h i nakon 4,5 h tretmana. Ovakvi uzorci su analizirani primenom ¹H NMR merenja uz potiskivanje signala vode u puferskom rastvoru pH 11,8. Može se pretpostaviti da tokom elektrolize 3-dehidro-deoksiholata dolazi do redukcije keto grupe prisutne u strukturi ispitivanog analita.</p><p>Na osnovu literaturnih podataka da neki od ciljnihmakrolidnih antibiotika kao &scaron;to je npr. azitromicin pokazuju oksidativno pona&scaron;anje na elektrodi od ugljenične paste i elektrodi od zlata deteljna karakterizacija i određivanje&nbsp; četiri makrolidna antibiotika rađena je primenom&nbsp; asične&nbsp;elektrode od ugljenične paste (CPE) koja se sastoji samo od grafitnog praha i parafinskog ulja sa optimizovanih direktnih anodnih SWV metoda. U slučaju EES-a i AZI-a diferencijalna pulsna voltametrija (DPV) je testirana za iste svrhe. Ključni&nbsp; parametar u slučaju razvoja analitičkih voltametrijskih metoda je odabir pH vrednosti pomoćnog elektrolita gde je oblik/simetričnost i intenzitet oskidacionog pika glavni kriterijum prilikom odabira. Kao odgovarajuće pH vrednosti za voltametrijsko određivanje EES-a primenom SWV metode odabrana je pH 8,0 sa E_p na 0,83<br />V u odnosu na ZKE, dok u slučaju DPV metode pH 12,0 sa&nbsp; E_p na 0,55 V u odnosu na ZKE je bila najpogodnija za analitičke svrhe. Za određivanje AZI-a, u slučaju obe SWV i DPV metode pH 7,0 se pokazala najpogodnijom sa E_p analitičkog signala na 0,85 V odnosno 0,80 V u odnosu na ZKE, dok u slučaju CLA i ROX koji su ispitivani samo primenom SWV metode za analitičke svrhe pH 12,0 je bila najpogodnija sredina sa E_p analitičkog signala na 0,65 V odnosno na 0,63 V&nbsp;u odnosu na ZKE. Postignute granice detkcije primenom nemodifikovane CPE i direktne anodne SWV su uglavnom u submikrogramskom koncentracionom opsegu 0,17 &micro;g mL^-1 , 0,32&nbsp; &micro;g mL^-1 i 0,30&nbsp; &micro;g mL^-1, u slučaju EES-a, AZI-a i ROX-a i u niskom mikrogramskom koncentracionom opsegu 1,43&nbsp; &micro;g mL^-1 za CLA. Razvijena SWV metoda sa jednostavnom CPE pokazala se pogodnom za određivanje ROX-a u komercijalnom proizvodu Runac^&reg; tableti. U slučaju optimizovanih DPV metoda postignute granice detekcije za EES i AZI su u niskom mikrogramskom&nbsp; koncentracionom opsegu 1,03&nbsp; &micro;g mL^-1 odnosno 1,53&nbsp; &micro;g&nbsp; mL^-1 . U želji da se&nbsp;postigne niža granica detekcije za AZI, DPV metoda&nbsp; je testirana u kombinaciji sa&nbsp; CPE radnom elektrodom povr&scaron;inski modifikovanom sa zlatnim nanočesticama&nbsp; prečnika 10 nm (Au-CPE) i&nbsp; postignuta granica detekcije je 0,95&nbsp; &micro;g mL^-1 sa&nbsp; E_p analitičkog signala na 0,80 V u odnosu na&nbsp; ZKE. RSD metode u slučaju Au-CPE je 3,5%, dok je u slučaju nemodifikovane CPE 6,0%.&nbsp; Linearnost analitičke metode zasnovane na primeni Au-CPE je dva puta &scaron;ira nego u slučaju&nbsp; primene nemodifikovane CPE.</p><p>Na osnovu dobijenih rezultata može se zaključiti da&nbsp; odgovarajuće kombinacije&nbsp; optimizovanih voltametrijskih tehnika sa ekolo&scaron;ki prihvatljivim i lako primenljivim radnim&nbsp; elektrodama, kao &scaron;to su Hg(Ag)FE, BiF-GCE i CPE zajedno sa Au-CPE, rezultuju razvojem&nbsp; pouzdanih analitičkih metoda, kako u oksidacionim tako i u redukcionim proučavanjima, koje&nbsp; često omogućuju&nbsp; određivanje tragova analita od farmakolo&scaron;kog značaja u jednostavnim, a u&nbsp;nekim slučajevima i u složenim sistemima.&nbsp;</p> / <p>Nowadays in different analytical laboratories there is the increasing number of analytical protocols, either based on highly sophisticated or simpler measurements techniques, which serving for determination of different target analytes of pharmacological importance. Among such target groups of the analyte belongs the antibiotics which present a great discovery in the field of medicine and thanks to them were saved more than seven million people but beside to the mentioned great benefits, antibiotics can cause a large number of side effects and bile acids together with their derivatives which are physiological detergents but if their concentration is not<br />controlled they can be cytotoxic to the body. In the present doctoral dissertation the development of analytical methods, primarily analytical voltammetric methods in combination with simple and contemporary electrodes/sensors, for the determination of selected analytes as antracycline antibiotic doxorubicin (DOX), macrolide antibiotics erythromycin ethylsuccinate (EES), azithromycin (AZI), clarithromycin (CLA) and roxithromycin (ROX) and 3-dehydrodeoxycholic acid were performed.</p><p>Voltammetric characterization and determination of the above mentioned antibiotics using a renewable silver-amalgam film electrode (Hg(Ag)FE) was performed by direct cathodic square-wave voltammetry (SWV) and by highly sensitive adsorptive square-wave voltammetry (SW-AdSV) in aqueous Britton-Robinson buffer solutions as supporting electrolyte covering the wider pH range. The Hg(Ag)FE response of DOX was monitored in the potential range between -0.20 and -0.80 V. For the trace level analysis the method optimization showed that the optimal conditions for the analytical peak with peak potential (E_p) at -0.57 V vs. SCE were: the pH 6.0, the accumulation potential -0.20 V, and the accumulation time 140 s. In the model solutions, DOX was determined in the concentration range of 4.99-59.64 ng mL^-1. The developed SWAdSV method was applied for the determination of DOX in spiked human urine sample. The lowest concentration of DOX of 9.89 ng mL^-1 in voltammetric vessel was determined with the relative standard deviation (RSD) less than 6%. As for the investigated macrolides, they showed reduction signals in fairly negative potential range. During direct cathodic SWV investigations conducted over the potential range from -0.75 V to -2.00 V vs. SCE, either one or two reduction peaks were obtained in the&nbsp; potential range from -1.5 to -1.9 V. For analytical purposes concerning the development of direct cathodic SWV and adsorptive stripping SWV methods the neutral&nbsp; and slightly alkaline media were suitable as pH 7.0 with E_p at -1.67 V vs.&nbsp; SCE for ROX and EES and pH 7.2 and pH 7.4 with E_p at -1.85 V and -1.64 V vs. SCE for AZI and CLA, respectively. Based on the cyclic voltammograms recorded at these pH values, adsorptioncontrolled electrode kinetics process can be proposed for all four investigated compounds. The water suppressed ¹H NMR measurements in the pH range between 6.0 and 10.5 indicated that the macrolide molecules at the optimal analytical conditions are predominantly in protonated form via their tertiary amino groups which supported in all four cases their adsorption on the appropriately polarized Hg(Ag)FE electrode. The optimized direct cathodic SWV methods showed good linearity in concentration ranges 4.81-23.3 &mu;g mL^-1, 4.53-29.8 &mu;g mL^-1, 1.96-28.6&nbsp; &mu;g mL^-1, and 1.48-25.9 &mu;g mL^-1 for AZI, EES, CLA and ROX, respectively. The SW-AdSV methods resulted in the linear responses at lower concentration ranges as 1.0-2.46 &mu;g mL^-1, 0.69- 2.44 &mu;g mL^-1, 0.05-0.99 &mu;g mL^-1 and 0.10-0.99 &mu;g mL^-1, for AZI, EES, CLA and ROX, respectively. The RSD for all developed methods was not higher than 1.5% except the SWV method for AZI with 4.7%. The direct cathodic SWV method was successfully applied for the determination of EES in the pharmaceutical preparation Eritromicin^&reg;, while SW-AdSV was tested in the case of the spiked urine sample and for determination of ROX in pharmaceutical preparation Runac^&reg;. In all above cases, the standard addition method was used. The reliability and accuracy of the above procedures in the case of EES determination in model system and pharmaceutical preparation Eritromicin^&reg; were validated by comparing them with those obtained by means of HPLC-DAD measurements.</p><p>After initial study of 3-dehydro-deoxycholic acid/3-dehydro-deoxycholate by glassy carbon electrode, where the absence of any reduction peak was observed in the Britton-Robinson buffer solutions between pH 5.0 and 11.8 by direct cathodic SWV, a bismuth-film was electrodeposited ex situ on the same glassy carbon electrode surface (BiF-GCE) from the usually used plating solution (0.02 mol L^-1 Bi(NO₃)₃, 1.0 mol L^-1 HCl and 0.5 mol L^-1 KBr) and such prepared film-electrode was applied for the characterization and determination of the the target analyte in alkaline media. The reduction signal of analytical importance was observed only by BiF-GCE in Britton-Robinson buffer solutions with pH values between 9.5 and 11.8 in adsorptive stripping square-wave voltammetry working regime, while in the case of the direct cathodic SWV experimental protocol only a very poor reduction peak was obtained. The optimized experimental conditions for the 3-dehydro-deoxycholate determination consist of the optimized electrode conditioning including the electrochemical cycling of the <em>ex situ </em>prepared BiF-GCE potentials in the potential span between -1.0 and -2.0 V vs. SCE (nearly 15 times) in the Britton-Robinson supporting electrolyte pH 11.8 till the stabilization of the baseline current, and the application of two key parameters of the adsorptive square-wave voltammetric protocol: the accumulation time as 30 s and accumulation potential as -1.0 V vs. SCE. Because of the relative asymmetry of the obtained reduction signals of the target analyte with peak E_p at -1.35 V vs. SCE, which is still present in the case of the SW-AdSV, the quantification of the target analyte was based on the linear correlation between peak area of the reduction signal and its appropriate concentrations, and reached limit of detection is 1.43 &mu;g mL^-1 and with two linear ranges of calibration curve from 4,76 &mu;g mL^-1 to 13.0 &mu;g mL^-1 and from 13,0 &mu;g mL^-1 to 23,1 &mu;g mL^-1 for the development of analytical method. The RSD of the method&nbsp; was 3.22%. Additional experiments were performed applying GCE with rectangular form (area 35.32 cm²) modified with ex situ prepared bismuth-film for the electrolysis of the target analyte which was performed at the potential -1.55 V (nearly the peak maxima of the target analyte) vs. SCE. The solution of interest was sampled at the beginning of the experiment, after 2.5 h and after 4.5 h of treatment. Such samples were analysed by simply water suppressing ¹H NMR measurements in the buffered solution at pH 11.8. It can be assumed that during electrolysis of 3-dehydrodeoxycholate the reduction of the keto group present in the structure of the target analyte can be occurred.</p><p>Driven by earlier literature data about the fact that some of the target macrolide antibiotics as e.g. azithromycin showed oxidation behavior at a carbon paste and gold working electrodes detailed characterization and determination of four target macrolide antibiotics were performed on classical carbon paste electrode (CPE) constituted only from graphite powder and paraffin oil with optimized direct anodic SWV methods. In the cases of EES and AZI differential pulse voltammetric (DPV) methods were tested for the same purpose as well. The key parameter in the case of the development of the analytical voltammetric methods is the selection of the pH value of the supporting electrolyte where the shape/simmetry and intensity of the oxidation peak were the criteria. As the appropriate pH value for determination of EES by SWV method the pH 8.0 was selected with E_p at 0.83 V vs. SCE while in the case of the DPV method the pH 12.0 with E_p at 0.55 V vs. SCE was the most suitable for analytical&nbsp; purpose. As for AZI determination, in the case of both SWV and DPV methods the pH 7.0 was the most appropriate supporting electrolyte with the Ep of analytical signal at 0.85 V and 0.80 V vs. SCE, respectively, while in the case of CLA and ROX which were investigated only with SWV method for the analytical purposes the pH 12.0 was the most suitable with E_p at 0.65 V and at 0.63 V vs. SCE. The obtained detection limits applying the bare CPE and the direct anodic SWV are mainly&nbsp; in submicrogram concentration range as 0.17 &mu;g mL^-1; 0.32 &mu;g mL^-1 and 0.30 &mu;g mL^-1 for EES, AZI, and ROX and in the low microgram concentration range as 1.43 &mu;g mL^-1 for the CLA, respectively. The developed method succesfully tested for the determination of ROX in the commercial formulation, Runac^&reg; tablet. In the case of the optimized DPV methods the obtained detection limits for EES and AZI are in the low microgram concentration range 1.03 &mu;g mL^-1 and 1.53 &mu;g mL^-1, respectively. For the improvement of the sensitivity for AZI the DPV method was tested in combination with a&nbsp; CPE working electrode surface modified with gold nanoparticles with diameter of 10 nm (Au-CPE) and reached the limit of detection was 0.95 &mu;g mL^-1 at E_p of 0.80 V vs. SCE. The RSD of the method in the case of the Au-CPE is 3.5% while in the case of the native CPE 6.0%. The linearity of the Au-CPE based analytical method is twice wider then it is case with the bare CPE applying protocol.</p><p>Based on the obtained results it can be conclude that the appropriate combination of the optimized voltammetric pulse techniques and the environmentally friendly and easy to use working electrodes as Hg(Ag)FE, BiF-GCE and CPE together with Au-CPE resulted in the development of reliable analytical method either in the oxidation or reduction studies, often allowing trace level determination of pharmacological importance target analytes in simpler and in some case complexes systems.</p>